UNIVERSITY OF SOUTHERN MINDANAO

CHEMICAL BIOLOGY II
ANALYTICAL CHEMISTRY
2ND Semester
A.Y 2022-2023
 Topic Outline
GRAVIMETRIC METHOD OF ANALYSIS
1. Precipitation Gravimetry
a) Applications
2. Volatilization Gravimetry

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Gravimetry
It is a group of analytical
methods in which the amount
of analyte is established
through the measurement of
the mass of a pure substance
containing the analyte.

The term gravimetric pertains

to weight measurement
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2 Types of Gravimetry
Precipitation Gravimetry – analyte
must first be converted into a solid
precipitate by precipitation with
appropriate precipitating agent. The
precipitate later from the solution is
filtered, washed, purified (if needed)
and weighed.

Volatilization Gravimetry – in this

method the analyte are volatilized
(dried) and then collected and
weighed, the mass of the volatilized
product is determined indirectly by
the loss of mass of the sample
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Steps required in gravimetric analysis,
after the sample has been dissolved,
can be summarized as follows:

1. Preparation of the
solution
2. Precipitation
3. Digestion
4. Filtration
5. Washing
6. Drying or igniting
7. Weighing and Calculation

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 Steps in Gravimetry
1. Preparation of the solution. This may involve several steps including
adjustment of the ph of the solution in order for the precipitate to
occur quantitatively and get a precipitate of desired properties,
removing interferences, adjustment of the volume of the sample to
suit the amount of precipitating agent to be added.
2. Precipitation: this requires addition of a precipitating agent solution
to the sample solution.
3. Digestion of the precipitate: the precipitate is left hot (below boiling)
for 30 min to 1 hr in order for the particles to be digested. Digestion
involves dissolution of small particles and reprecipitation on larger
ones resulting in particle growth and better and precipitate
characteristics
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 Precipitation Gravimetry
Properties of Precipitates and Precipitating agents
1. Easily filtered and washed free of contaminants
2. Sufficiently low solubility that no significant loss of the analyte
occurs during filtration and washing
3. Unreactive with constituents of the atmosphere
4. Known chemical composition after drying or igniting

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4. Filtering and washing the precipitate: It is crucial to wash the precipitate
very will in order to remove all adsorbed species which will add to weight
of precipitate. One must be careful not to use much water since part of the
precipitate may be lost. Also, in case of colloidal precipitates, we should
not use water as washing solution since the peptization would occur. Dilute
nitric acid, ammonium nitrate or dilute acetic acid may be used.

5. Drying and ignition: The purpose of drying (heating at about 120-150

degree Celsius) in an over or ignition in a muffle furnace at temperatures
ranging from 600-1200 degree Celsius is to get a material with exactly
known chemical structure so that the amount of analyte can be accurately
determined.
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Determination of
Calcium in Water

9
Water Sample

Add oxalic acid ( H2C2O4)

Ammonia is added

The Calcium Oxalate precipitate is filtered and

weighed

Ignited

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 Example 5.1
The Calcium in 2.00-ml sample of a natural water was determined by
precipitating the cation as CaC2O4. The precipitate was filtered,
washed, and ignited in a crucible with an empty mass of 26.6002 g.
The mass of the crucible plus CaO (56.077 g/mol) was 26.7134 g.
Calculate the concentration of Ca (40.078 g/mol) in water in units if
grams per 100 ml of the water.

Solution:

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 Advantages of Gravimetric analysis
• Accurate and Precise
• Possible sources of errors can be checked: Gravimetric
analysis avoids problems with temperature fluctuations,
calibration errors, and any other problem associated with
volumetric analysis
• It is an absolute method
• Inexpensive

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 Disadvantages
• Proper technique is critical
• Careful and time consuming
• Scrupulously clean glassware
• Very accurate weighing
• Coprecipitation

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 Particle size
• 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 pure than

precipitates made up of fine particles. Steps required in gravimetric
analysis, after the sample has been dissolved.

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 Colloidal Precipitates and Crystalline Precipitates

1. Colloidal suspensions
- Tiny particles that are invisible to the naked eye ( 10^-7 to 2-^-4 cm
in diameter)
- Showed no tendency to settle from solution
- Not easily filtered

2. Crystalline suspension
- particles with dimensions on the order of tenth of a millimeter or
greater
- temporary dispersion of such particles of a tend to settle
spontaneously
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- Easily filtered
 Impurities in Precipitates
1. Occlusion : some constituents of the precipitation medium may be
trapped in the crystal structure resulting in positive or negative errors.
The trapped materials can be water, analyte ions, precipitating agent
ions, or other constituents in the medium. Slow addition of
precipitating agent and stirring may avoid occlusion but if it does
occur, dissolution of precipitate and reprecipitation may have to be
done.

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2. Inclusion: if the precipitation medium contains ions of the same
charge and size as one forming the crystal structure of the precipitate,
this extraneous ion can replace an ion from the precipitate in the
crystal structure.
Example:
In the precipitation of NH4MgPO4 in presence of K+ , ammonium
leaves the crystal magnesium ammonium phosphate and is replaced
by K+ since both have the same charge of positive 1 and size
However, the mass of Ammonium ion is 18 while that of potassium ion
is 39. In this case a positive error occurs as the weight of precipitate
will be larger when potassium replaces ammonium ion.
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3. Surface adsorption: This always results in positive errors in
gravimetric procedures. See previous discussion on colloidal
precipitates

4. Postprecipitation: In cases where there are ions other than analyte

ions which form precipitates with the precipitating agent but at much
slower rate than analyte, if the precipitate of the analyte is left for a
long time without filtration then the other ions start forming a
precipitate over the original precipitate leading to a positive error.
Example: Include precipitation of copper as the sulfide in presence of
zinc. Copper sulfide is formed first but if not directly filtered, zinc sulfide
starts to precipitate on the top of it. The same is observed in the
precipitation of calcium as the oaxalate in the presence of magnesium.
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 Application
• Inorganic
• Inorganic ash content of an organic material
• Determination of dissolved solids in natural waters wastewaters
• Determining the moisture in a variety of products

Organic
• Alkaline metals and earths in organic materials
• Determine biomass in waters and wastewaters

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 Sample problem 5.2
An iron-ore was analyzed by dissolving a 1.1324-g sample in
concentrated HCL. The resulting solution was diluted with water, and
the iron (III) was precipitated as the hydrous oxide Fe2O3∙ x H2O by the
addition of NH3. After filtration and washing, the residue was ignited at
a high temperature to give 0.5394 g of pure Fe2O3 (159.69 g/mol).
Calculate (a) the % Fe (55.8847 g/mol) and (b) the % Fe3O4 (231.54
g/mol) in the sample.

Solution:

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 Sample problem 5.3
• A 0.3516 g sample of commercial phosphate detergent was ignited at
a red heat to destroy the organic matter. The residue was then taken
up in hot HCl which converted to P to H3PO4. The phosphate was
precipitated with Mg2+ followed by aqueous NH3 to form
MgNH4PO4∙6 H2O. After being filtered and washed, the precipitate
was converted to Mg2P2O7 (222.57 g/mol) by ignition at 100 degree
Celsius. This residue weighed 0.2151 g. Calculate the percent P
(30.974 g/mol) in the sample.

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 Sample problem 5.4
A 0.2356 g sample containing only NaCl (58.44 g/mol) and BaCl2 (208.23
g/mol) yielded 0.4637 g of dried AgCl (143.32 g/mol). Calculate the
percent of each halogen compound in the sample.

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