Gravimetric analysis

CDB 3093
Dr Asna Mohd Zain
RSci AMIChemE

Outline

Overview of gravimetric methods

Gravimetric calculation
Precipitation gravimetry
Solubility consideration
Impurities coprecipitation (inclusion, occlusion and adsorption)
Particle size control, S & Q
Filtration, rinsing, drying and igniting
Gravimetry results

Intro to gravimetric analysis

Mass based analysis rely on weighing products
and/or reactant before and after some chemical
reaction

A product of known composition is precipitated as an

insoluble product from a reaction mixture
The precipitate is filtered from the solution, dried and
weighted to find the mass of product.
1900s T.W. Richard and colleagues winning Nobel
prize for gravimetric analysis by measuring atomic
mass of Ag, Cl and N to six figure accuracy.
Gary Christian, Analytical Chemistry,

6th Ed. (Wiley)

Titration is a tried-and-true technique, capable of high precision and accuracy.

Gravimetric calculation
The fundamental of gravimetric analysis is by understand all the chemical reactions its
balance equation to perform stoichiometric calculations by knowing their:

The concentration, ppm, ppb

Moles of compound, mol
Molarity of compound, M
Weight percent, wt %
Molecular mass/ formula mass (FM)

Concentration in ppm or ppb

ppm = g/mL =mg/L
[wt solute (g)/vol sample (mL)]x106

ppb = ng/mL = g/L

[Wt solute (g) / vol sample (mL)]x109

Gravimetric calculation
Moles/molarity

Ag+ + Cl- AgCl(s)

Unknown Cl- is titrated with Ag+, equilibrium constant, k of 5.6 x 109

Rapid reaction forming AgCl in solid form.
If, 10 mL of chloride solution (measured by tranfer pipet) requires 22.97 mL of
0.052 74 M AgNO3 (delivered by a buret) for a complete reaction.
What are concentration of Cl- in the unknown?
Mol Ag+ = vol x molarity = (0.02297 L)(0.05274 mol/L)

= 0.001211 mol

I mol of Cl- react with I mol of Ag+, if 0.001211 mol of Ag+ is required,
then 0.001211 mol of Cl- must be in 10 mL of unknown, therefore:
Cl- unknown = mol Cl- /L of unknown = 0.001211 mol/ 0.01 L = 0.1211 M

Gravimetric calculation
The solution titrated was made by dissolving 1.004 g of unknown solid in a
total volume of 100 mL.
What is the weight percent of chloride (Cl-) in the solid?
10 mL of unknown contain 0.001211 mol of Cl- Therefore, 100 mL must
contain 10 times as much, or 0.01211 mol of Cl Cl- weight = (0.01211 mol Cl-)(35.4527 g/mol Cl-) = 0.4294 g Cl

Weight percent of Cl- in the unknown:

Wt % [Cl-]
= (g Cl-)/(g unknown) x 100
= (0.4297 g Cl-)/(1.004 g unknown) x 100
= 42.78 wt %

For the diluted concentration

[Ag]conc x Vconc = [Ag]diluted x Vdiluted

Gravimetric calculation
Normality is equivalent of material per liter of solution

N = eq/L or meq/mL

Eq = mol x no. of reacting units per molecule

E.g.: eq = mol x 1 reacting unit of Hydrogen per molecule of HCl

eq. wt. is the weight of substance (g) to furnish one mole of reacting unit.

Example:

Calculate the equivalent weight of the following substances

(a) NH3 and (b) H2C2O4 (in reaction with NaOH).

Answer:
(a) Eq wt = (NH3 g/mol)/(1 eq/mol) = 17.03/1 = 17.03 g/eq

(b) Eq wt = (H2C2O4 g/mol )/ (2 eq/mol) = 90.04/2 = 45.02 g/eq

Note: reacting unit is the H in acid or OH- in base

eq is applicable in oxidation and reduction reaction

Direct and indirect gravimeticy

analysis
Direct analysis
the total suspended solids in the water (filtration)
If the analyte is not a solid (Pb2+)? convert it into a solid form

If we add HgCl2 in excess, each mole of PO33- produces one mole of

Hg2Cl2. The precipitates mass, therefore, provides an indirect
measurement of the amount of PO33 in the original sample.

Precipitation gravimetry
In precipitation gravimetry, an insoluble compound forms, when we add a
precipitating reagent, or precipitant, to a solution containing our analyte.
Add precipitating reagent to sample solution
Reacts with analyte to form insoluble material
Precipitate has known composition or can be converted to known
composition
Precipitate handling involves

Quantitative collection (no losses)

Isolation of pure product
Measure mass of precipitate
Calculation of original analyte content (concentration)

Solubility consideration
An accurate precipitation gravimetric method requires that
the precipitates solubility be minimal
Solubility losses are minimized by carefully controlling the
composition of the solution in which the precipitate forms.
Requires an understanding of the relevant equilibrium
reactions affecting the precipitates solubility

Solubility consideration
Solubility losses may be minimized by adding a large excess of Cl

Ag+ also form a series of soluble chloro-complexes, therefore:

Increasing the concentration of chloride, however, leads to an increase in the solubility
of AgCl due to the soluble chloro-complexes large excess of chloride must be
avoided
(Note Ksp is solubility product constant, Kosp for AgCl = 1x10-10)

 ph Effect

Solubility consideration

When the pH is greater than 12.4, the predominate phosphate species is PO43, and the
solubility of Ca3(PO4)2 will be at its minimum because only the first reaction occurs.
As the solution becomes more acidic, the solubility of Ca3(PO4)2 increases due to the
contributions of the 3 other reactions.
Q1: What must be the concentration of added Ag+ to just start precipitation of AgCl in a 1.0 x
10-3 M solution of NaCl? Given the Ksp of AgCl at 25C is 1.0 x 10-10.

Impurities
Precipitation gravimetry is based on a known stoichiometry
between the analytes mass and the mass of a precipitate.
Any impurities present in the precipitates matrix must be
removed before obtaining its weight.
the precipitate must be free from impurities

Impurities coprecipitation
Three main mechanisms of coprecipitation
Inclusion

Adsorption

Occlusion

Impurities

Ostwalt ripening

Inclusions are difficult to remove since the included material is chemically part of the
crystal lattice. The only way to remove included material is through reprecipitation.
Reprecipitate occur by small particle tend to dissolve and attached to the surface of larger
particle or individual particles agglomerate to share common counter ions layer
Occlusions are minimized by maintaining the precipitate in equilibrium with its supernatant
solution for an extended time. This process is called digestion.
One benefit of digestion (Ostwald ripening) is that it also increases the average size of
precipitate particles or crystal
Surface adsorption is minimized by decreasing the precipitates available surface area.
But colloidal particles (size 1-100 m) promote surface adsorption

Impurities
Silver chloride colloidal particle and adsorptive layers when
Cl- is in excess

Impurities
The formation of these additional precipitates can usually be minimized by
carefully controlling solution conditions
Interferents forming precipitates that are less soluble than the analyte
may be precipitated and removed by filtration, leaving the analyte behind in
solution.

Either the analyte or the interferent can be masked using a suitable reagent,
preventing its precipitation.
Post precipitation occurs when the precipitate allow to stand in contact with
mother liquor producing second substance e.g. calcium oxalate precipitated
in the presence of magnesium ions forming magnesium oxalate.

Particle size control

By carefully controlling the precipitation reaction we can significantly increase a
precipitates average particle size.
Precipitation consists of two distinct events:
Nucleation: the initial formation of smaller stable
particles of precipitate (Nuclei).
Particle growth: Larger particles form combination of ions/molecules with the
existing nuclei (when the rate of particle growth exceeds the rate of nucleation).

Particle size control

Supersaturation, where more dissolved salt in solution than in equilibrium, a metastable condition, is
driving force for equilibrium before nucleation occur
Solutes relative supersaturation, RSS, expressed as:
Q = solutes actual concentration, S = solutes expected concentration at equilibrium (solubility). RSS is
the von Weimarn ratio.
When RSS is small, precipitation is more likely to occur by particle growth than by nucleation. High RSS
promote small crystal but low RSS lead to large crystal.

Temperature and pH are useful ways to increase the value of S, precipitate from hot solution or used
low pH value where acid medium reduce rate of precipitation.
Conducting the precipitation in a dilute solution of analyte, or adding the precipitant slowly and with
vigorous stirring are ways to decrease the value of Q.

Particle size
control
Surface adsorption of excess lattice ions, however, provides the
precipitates particles with a net positive or negative surface charge.
Electrostatic repulsion between the particles prevents them from
coagulating into larger particles.
Coagulation can be induced by increasing the concentration of the ions
responsible for the secondary adsorption layer or by heating the solution.
One way to induce coagulation is to add an inert electrolyte, which
increases the concentration of ions in the secondary adsorption layer

Filtration of precipitate
Preparation of solution

Using a filter paper,

crucible and a
vacuum pump,

Precipitation

Digestion

Filtration

Separate solid
precipitate and
solution by filtration
to produce a solid
products and
filtrate in flask

Washing

Drying or igniting

Weighing

Calculation

Rinsing the precipitate

Involves the use of cold solvents or rinse solutions containing organic
solvents such as ethanol. Precipitates containing acidic or basic ions
may experience solubility losses if the rinse solutions pH is not
appropriately adjusted .
A volatile inert electrolyte is often added to the rinse water to prevent
the precipitate from reverting into smaller particles that may not be
retained by the filtering device.

This process of reverting to smaller particles is called peptization.

The volatile electrolyte is removed when drying the precipitate.

Drying or igniting the precipitate

After filtration, a gravimetric precipitate is heated until its mass becomes constant.
Ignition decomposes the solid and form a compound of known composition.
A temperature of 110 C is usually sufficient when removing water and other easily
volatilized impurities.
https://youtu.be/rZMzGxjvklo
https://youtu.be/dERZhN-01f8

Cations based precipitation

Anions based precipitation

Application

Gravimetric methods have been developed for most inorganic anions

and cations as well as neutral species such as water, sulfur dioxide,
carbon dioxide, and iodine.
A variety of organic substances can also be easily determined
gravimetrically. Examples: lactose in milk products, salicylates in drug
formulations, nicotine in pesticides etc.
Organic precipitant

Gravimetric result
Gravimetry resulted in the following :
Percent of analyte, % A

= wt of analyte /wt of sample x 100

GF is gram of analyte per gram of ppt

GF = gravimetry factor = [FM analyte/ FM ppt] x a/b
Here,
a is mol of analyte
b is mol of precipitate (ppt)
FM is formula mass

Gravimetry factor

Summary

Gravimetry calculation
Advantages of gravimetry
Precipitation gravimerty
Solubility consideration
Impurities
Particle size control
Completing steps
Outcome result

Example calculation
Q2: An ore is analyzed for the manganese content by converting
the manganese to Mn3O4 and weighing it. If a 1.52 g sample
yields Mn3O4 weighing 0.126 g, what would be the percent Mn2O3
in the sample? The percent Mn? (3 mol Mn2O3 reactant and
product of 2 mol Mn3O4)

References
Gary D. Christian, 2003 Analytical Chemistry, 6th Ed., Wiley, QD101.2
C57 2003
Daniel C Harris, Exploring Chemical Analysis Second Ed., W.H
Freeman and Company, 2000 QD 75.2. H368.
Seamus P.J. Higson, Analytical chemistry, Oxford University Press,
2004 QD 101.2.H54