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Gravimetric Methods
of Analysis

A History of Gravimetric Analysis

Theodore W. Richards (1868 - 1928)
…at Harvard developed/refined many of the
techniques of gravimetric analysis of Ag and
Cl. These techniques were used to
determine the atomic wts of 25 of the
elements by preparing pure samples of the
Cl of the elements, decomposing known wts
of the compounds, and determining the Cl
content by gravimetric methods.

Richards became the first American to

receive the Nobel Prize in Chemistry in
1914.

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Gravimetric Analysis
Gravimetric analysis is the quantitative determination of analyte
concentration through a process of precipitation of the
analyte, isolation of the precipitate, and weighing the
isolated product.

Uses of gravimetric analysis…

– Chemical analysis of ores and
industrial materials
– Calibration of instrumentation
– Elemental analysis of
inorganic compounds

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Gravimetric Analysis
• 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.

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Gravimetric Analysis
• Accurate and precise.

• Possible sources of errors can be

checked.

• It is an ABSOLUTE method.

• Relatively inexpensive

Gravimetry encompasses all techniques in which

mass or a change in mass is measured.
ex:

When you step on a scale after exercising you are

making, in a sense, a gravimetric determination of your
mass.

Measuring mass is the most fundamental of all

analytical measurements, and gravimetry is
unquestionably the oldest analytical technique.

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Overview of Gravimetry
Gravimetry--Any method in which the signal is a
mass or change in mass.
This suggests that there are at least two ways to use
mass as an analytical signal.
• measure an analyte’s mass directly by placing it on a
balance and recording its mass.
ex. total suspended solids in water released
from a sewage-treatment facility. Suspended solids
are just that; solid matter that has yet to settle out of
its solution matrix.

The analysis is easy. Collect a sample and pass it

through a preweighed filter that retains the
suspended solids. After drying to remove any
residual moisture, weigh the filter.

The difference between the filter’s original mass and

final mass gives the mass of suspended solids. This
is a direct analysis because the analyte itself is the
object being weighed.

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What if the analyte is an aqueous ion, such as Pb2+?

In this case, the analyte cant be isolated by by filtration

because the Pb2+ is dissolved in the solution’s matrix.

•measure the analyte’s mass, by chemically converting

it to a solid form. If we suspend a pair of Pt electrodes
in our solution and apply a sufficiently + potential
between them for a long enough time, the reaction is
forced to go to completion:

Pb2+(aq) + 4H2O(l) t PbO2(s) + H2(g) + 2H3O+(aq)

The Pb2+ ion in solution oxidizes to PbO2 and

deposits on the Pt electrode serving as the anode.

Weigh the Pt anode before and after applying the

potential, the difference in the two measurements
gives the mass of PbO2 and, from the reaction’s
stoichiometry, the mass of Pb2+.

This also is a direct analysis because the material

being weighed contains the analyte.

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The indirect determination of moisture content in foods

is done by difference. The sample’s initial mass includes
the water, whereas the final mass is measured after
removing the water.

The analyte can be determined indirectly without its

ever being weighed. Again, as with the determination
of Pb2+ as PbO2(s), take advantage of the analyte’s
chemistry.

For example, phosphite, PO33–, reduces Hg2+

to Hg22+. In the presence of Cl– a solid precipitate of
Hg2Cl2 forms.

ex: PO33–, reduces Hg2+ to Hg22+. In the presence of Cl–

a solid precipitate of Hg2Cl2 forms.

2HgCl2(aq) + PO33–(aq) + 3H2O(l) Hg2Cl2(s) + 2H3O+(aq) + 2Cl–(aq)+ PO43–

(aq)

If HgCl2 is added in excess, each mole of PO33–

produces 1 mole of Hg2Cl2. The precipitate’s mass
provides an indirect measurement of the mass of
PO33– present in the original sample.

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Types of Gravimetric Methods

precipitation gravimetry—a gravimetric method in which the
signal is the mass of a precipitate.

Electrogravimetry--a gravimetric method in which the signal

is the mass of an electrodeposit on the cathode or anode in
an electrochemical cell.

volatilization gravimetry--A gravimetric method in which

the loss of a volatile species gives rise to the signal.

particulate gravimetry--A gravimetric method in which the

mass of a particulate analyte is determined following its
separation from its matrix.

When the signal is the mass of a ppt, the method is

precipitation gravimetry. The indirect determination of PO33– by
precipitating Hg2Cl2 is a representative example, as is the direct
determination of Cl– by precipitating AgCl.

In electrogravimetry the analyte is deposited as a solid film

on one electrode in an electrochemical cell. The oxidation of
Pb2+, and its deposition as PbO2 on a Pt anode is one example
of electrogravimetry. Reduction also may be used in
electrogravimetry.

The electrodeposition of Cu on a Pt cathode provides a direct

analysis for Cu2+.

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When thermal or chemical energy is used to remove a

volatile species, the method is volatilization gravimetry.

In determining the moisture content of food, thermal

energy vaporizes the H2O. The amount of C in an organic
compound may be determined by using the chemical energy
of combustion to convert C to CO2.

In particulate gravimetry the analyte is determined

following its removal from the sample matrix by filtration
or extraction. The determination of suspended solids is one
example of particulate gravimetry.

Gravimetry

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An accurate gravimetric analysis requires that the mass of

analyte present in a sample be proportional to the mass or
change in mass serving as the analytical signal.

All gravimetric methods proportionality involves a

conservation of mass.
Gravimetric methods involving a chemical reaction, the
analyte should participate in only one set of reactions,
the stoichiometry of which indicates how the
precipitate’s mass relates to the analyte’s mass.
For the analysis of Pb2+ and PO33– the following is the
conservation equations

For the analysis of Pb2+ and PO33– the following is the

conservation equations

Pb2+(aq) + 4H2O(l) ------ PbO2(s) + H2(g) + 2H3O+(aq)

Moles Pb2+ = moles PbO2

Moles PO33– = moles Hg2Cl2

2HgCl2(aq) + PO33–(aq) + 3H2O(l) ----Hg2Cl2(s) + 2H3O+(aq) + 2Cl–(aq)+ PO43–(aq)

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Removing the analyte from its matrix by filtration or

extraction must be complete. When true, the analyte’s
mass can always be found from the analytical signal;
thus, for the determination of suspended solids:

Filter’s final mass – filter’s initial mass = g suspended solid

for the determination of the moisture content

Sample’s initial mass – sample’s final mass = g H2O

Why Gravimetry Is Important

gravimetry is one of the techniques whose measurements
require only base SI units, such as mass and moles, and
defined constants, such as Avogadro’s number and the
mass of 12C.
The result of an analysis must ultimately be traceable to
methods, such as gravimetry, that can be related to
fundamental physical properties. Verifying a method by
analyzing a standard reference material is common.
Estimating the composition of these materials often
involves a gravimetric analysis.

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Precipitation Gravimetry
•based on the formation of an insoluble compound ff the
addition of a precipitating reagent, or precipitant, to a
solution of the analyte.

Precipitant---A reagent that causes the precipitation of a

soluble species.

In most methods the precipitate is the product of a

simple metathesis rxn between the analyte and
precipitant; however, any reaction generating a ppt can
potentially serve as a gravimetric method.

Gravimetric Analysis

• 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
coprecipitates.

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Gravimetric Analysis
• Accuracy
– Solubility Products.
– Solubility.
– Particle size.
– Coprecipitates.
– Drying and ignition.

Gravimetric Analysis

• Solubility Products
– Even the most insoluble products have at
least a certain solubility. It is therefore
more correct to call these compounds
sparingly soluble substances, eg: AgCl

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Gravimetric Analysis
• Solubility.
– Common ion effect
– Ionic strength
– Fractional precipitation
– Complex ions
– Temperature
– Solvent

Gravimetric Analysis
• Particle size.

– Colloidal suspension (10-6 - 10-4 mm diameter)

to crystalline precipitate.

– Depends on nucleation and particle growth.

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Gravimetric Analysis
• Coprecipitates.
– Removal during precipitation of compounds
which are otherwise soluble.
– Sources:
• Surface adsorption
• Mixed crystal formation
• Occlusion
• Mechanical entrapment

Theory and Practice

•precipitate must be of low solubility, high purity, and of
known composition if its mass is to accurately reflect the
analyte’s mass.
•precipitate must be in a form that is easy to separate
from the reaction mixture.
Solubility Considerations
•precipitate’s solubility be minimal.
•Many total analysis techniques can routinely be performed with
an accuracy of better than ±0.1%. To obtain this level of accuracy,
the isolated ppt must account for at least 99.9% of the analyte.
•By extending this requirement to 99.99% accuracy is not limited
by the precipitate’s solubility.

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Solubility losses are minimized by carefully controlling

the composition of the solution in which the ppt
forms. This requires an understanding of the relevant
equilibrium rxns affecting the precipitate’s solubility.

Ag+(aq) + Cl–(aq) ------ AgCl(s)

precipitant

Avoiding Impurities Precipitation gravimetry is based on a

known stoichiometry between the analyte’s mass and the mass
of a precipitate. It follows, therefore, that the precipitate must
be free from impurities.

Since precipitation typically occurs in a solution rich in dissolved

solids, the initial precipitate is often impure. Any impurities
present in the precipitate’s matrix must be removed before
obtaining its weight.

The greatest source of impurities results from chemical and

physical interactions occurring at the precipitate’s surface. A
precipitate is generally crystalline, even if only on a
microscopic scale, with a well-defined lattice structure of
cations and anions.

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inclusion -- Potential interfering ions whose size and charge

are similar to a lattice ion may substitute into the lattice
structure by chemical adsorption, provided that the
interferent precipitates with the same crystal structure.

The presence of an inclusion does not decrease the amount of

analyte that precipitates, provided that the precipitant is added
in sufficient excess. Thus, the precipitate’s mass is always larger
than expected.

Impurities in Precipitates
• Surface adsorption
– Unwanted material is
adsorbed onto the surface
of the precipitate Particle Volume
Scaling per Particle
Particle Surface Area
10000
– Digestion of a precipitate Particle Volume = 4/3(r )
3
Particle Surface Area (nm )
2

reduces the relative 8000

2
Particle Surface Area = 4(r )

surface area and, 6000

therefore, the area Particle Volume

available for adsorption of 4000

impurities 2000

– Washing can remove Particle Surface Area

0
impurities bound to the
surface 0 2 4 6 8 10 12 14
Particle Radius (A.U.)

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Impurities in Precipitates
• Coprecipitation…
…is the precipitation of an unwanted species along with
your analyte of interest;
… occurs to some degree in every gravimetric analysis;
• A major factor for precipitations of barium sulfate and those
involving hydrous oxides

… and cannot be avoided, but can be minimized by

careful precipitation and a thorough washing of the
precipitate.

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Increasing Purity
• Re-precipitation
– a procedure including washing away the mother liquor,
redissolving the precipitate, and precipitating the
product again
• Drying the solid
– Generally the solids are dried at
~120 oC, but conditions for
drying can vary considerably. To
determine the correct drying regime,
a thermogravimetric (TGA) balance may be used.

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Increasing Purity
• Precipitation in the presence of electrolyte
– Coulombic repulsion is diminished in the presence of
electrolyte because of a compression of the volume of
the ionic atmosphere

• Digestion
– Raising the temperature will increase the collision
energy for colloidal particles and overcome Coulombic
repulsion, leading to formation of larger particles
(coalescence)

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More Terminologies
occlusion
A coprecipitated impurity trapped within a ppt as it
forms.
digestion
The process by which a ppt is given time to form larger,
purer particles.
adsorbate
A coprecipitated impurity that adsorbs to the surface of
a ppt.
inclusion
A coprecipitated impurity in which the interfering ion
occupies a lattice site in the precipitate.

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relative supersaturation -- A measure of the extent to which a

solution, or a localized region of solution, contains more
dissolved solute than that expected at equilibrium (RSS).

homogeneous precipitation-- A precipitation in which the

precipitant is generated in situ by a chemical reaction.
coagulation
The process of smaller particles of precipitate clumping together
to form larger particles.

Supernatant-- The solution that remains after a

precipitate forms.
peptization
The reverse of coagulation in which a coagulated precipitate
reverts to smaller particles.

• Adsorption is a process in which a substance (gas,

liquid, or solid) condenses onto the surface of a solid
• The electric double layer of a colloid consists of a
layer of charge associated with the surface of the
particles and a layer with a net opposite charge in the
solution surrounding the particles
• A colloid is a finely divided particle (typically with
diameters from 10 nm to 1 mm) that forms a stable
dispersion within a medium (air or liquid)

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Mechanism of Precipitation
• Induction period
– The time before nucleation occurs after the addition of
the precipitating agent to the solution
– May range from milliseconds to several minutes
• Nucleation
– Formation of small, stable aggregates or nuclei of
precipitate
– Nuclei have sizes down to ~1 nm, composed of a few
atoms, and there may be up to 1010 nuclei per mole of
analyte
– Excess ions from solution collect around the nuclei

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Mechanism of Precipitation
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
ones grow (Ostwald ripening). This process helps
produce larger crystals that are more easily filtered
from solution

DT

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Ideal Analytical Precipitation

• In an ideal world, an analytical precipitate for gravimetric
analysis should consist of perfect crystals large enough to
be easily washed and filtered.
– The perfect crystal would be free from impurities and
be large enough so that it presented a minimum
surface area onto which foreign ions could be
adsorbed.
• The precipitate should also be "insoluble" (i.e., low
solubility such that loses from dissolution would be
minimal).

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Summary
• Principles
– Solution reaction between analytes and reagents to
give sparingly soluble products.
– Drying or ignition of precipitates.
– Weighing

• Apparatus
– Flasks, beakers, pipettes, crucibles and filter papers.
– Oven or furnace and a dessicator.
– Analytical quality balance.

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Summary

• 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

Summary

• Disadvantages
– Careful and time consuming.
– Scrupulously clean glassware.
– Very accurate weighing.
– Coprecipitation.

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Criteria for Gravimetric Analysis

1. The desired substance must completely
precipitate from solution
• In most determinations the precipitate is of
such low solubility that dissolution of the
analyte is negligible
• An additional factor is the "common ion"
effect, further reducing the solubility of the
precipitate

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Criteria for Gravimetric Analysis

1. The desired substance must completely
precipitate from solution
• In most determinations the precipitate is of
such low solubility that dissolution of the
analyte is negligible
• An additional factor is the "common ion"
effect, further reducing the solubility of the
precipitate

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Criteria for Gravimetric Analysis

When Ag+ is precipitated from solution through

the addition of Cl-

Ag   Cl   AgCl (s )

the (low) solubility of AgCl is further reduced by

the excess of Cl- that is added, pushing the
equilibrium to the right (Le Chatelier’s Principle).

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Criteria for Gravimetric Analysis

2. The weighed form of the product should be of
known composition.
3. The product should be "pure" and easily
filtered.
• It is usually difficult to obtain a product that is "pure“
(i.e., one that is free from impurities)
• Careful precipitation and sufficient washing may
reduce the level of impurities

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Conditions for Analytical Precipitation

• Precipitation from hot solution
– The molar solubility (S) of precipitates increases with
an increase in temperature
– An increase in S decreases the supersaturation and
increases the size of the particle.
• Precipitation from dilute solution
– This keeps the molar concentration of the mixed
reagents low. Slow addition of precipitating reagent
and thorough stirring keeps Q low. (Uniform stirring
prevents high local concentrations of the precipitating
agent.)

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Conditions for Analytical Precipitation

• Precipitation at a pH near the acidic end of the
pH range in which the precipitate is quantitative.
– Many precipitates are more soluble at the lower (more
acidic) pH values and so the rate of precipitation is
slower.
• Digestion of the precipitate.
– The digestion period can lead to improvements in the
organization of atoms within the crystalline nuclei,
such as expulsion of foreign atoms (or other
impurities).

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Gravimetric Analysis
A 10.0 mL solution containing Cl- was treated with
excess AgNO3 to precipitate 0.4368 g of AgCl.
What was the concentration of Cl- in the unknown?
(AgCl = 143.321 g/mol)
Number of moles of Cl- = number of moles of AgCl

0.4368g
  3.048 10 - 3 mol
143.321g/mol

3.048 10 3 mol

Concentration of Cl-   0.3048 M
0.01000 L
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Other Analytes

Why is the form weighed different from the precipitate?

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Sample Calculation
• Reaction:
aA + rR -----> AaRr ppt
where:
– a is # of moles of analyte A
– r is # of moles of reagent R
– AaRr is a pure, insoluble precipitate
which we can dry and weigh or ignite
to convert to something we can weigh
– ppt=precipitate
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The Gravimetric Factor

• G.F. = a FW[analyte]
b FW[precipitate]

• Analyte ppt G.F.

CaO CaCO3
FeS BaSO4
UO2(NO3)2.6H2O U3O8
Cr2O3 Ag2CrO4

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What Do We Get Out of Gravimetry?

• % of analyte, % A

• %A = weight of analyte x 100

weight of sample

• weight of ppt directly obtained ->?A

Gravimetric Factor

• Analyte ppt G.F.

CaO CaCO3 CaO/CaCO3
FeS BaSO4 FeS/BaSO4
Cr2O3 Ag2CrO4 Cr2O3/2Ag2CrO4

• Naming is critically important

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Why AgCl?

• Reaction is highly selective - no

interferents
– 2AgCl ----> 2Ag + Cl2(g)

• AgCl is insoluble in water, i.e., only

slightly soluble in water-losses
negligible

Why AgCl is a Good Precipitate?

• Small mass of analyte yields large mass of
precipitate-sensitive technique

• AgCl precipitates in curds/lumps that can

be easily collected, dried, and weighed

• Precipitate (ppt) is not hygroscopic

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Problem
• Consider a 1.0000 g sample containing 75%
potassium sulfate (FW 174.25) and 25% MSO4.
The sample is dissolved and the sulfate is
precipated as BaSO4 (FW 233.39). If the BaSO4
ppt weighs 1.4900, what is the atomic weight
of M2+ in MSO4?
• ANS: Mg2+

Answer
• The hard part is setting up the correct
equation (good stoichiometry skills are
essential here!):
0.75 * 233.39 0.25 * 233.39
1.4900  
174.25 x  96.06
• Rearranging and solving:
58.3475 2
0.4855  ; x  24.12( Mg )
x  96.06

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Problem
• A mixture of mercurous chloride (FW 472.09) and
mercurous bromide (FW 560.99) weighs 2.00 g. The
mixture is quantitatively reduced to mercury metal
(At wt 200.59) which weighs 1.50 g. Calculate the %
mercurous chloride and mercurous bromide in the
original mixture.
• ANS: 0.5182 g

Answer
• Again, important to set up correct equation:
2 * 200.59 * x 2 * 200.592  x 
1.50  
472.09 560.99
• Rearranging and solving:

0.8498  0.71512  x   1.50

x  0.5182 g

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Sample Calculation
When an sample of impure potassium
chloride (0.4500g) was dissolved in water and
treated with an excess of silver nitrate, 0.8402
g of silver chloride was precipitated. Calculate
the percentage KCl in the original sample.

(Answer: 97.12 %)

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Determination of Mg2+ in Water and Wastewater

Description of Method. Magnesium is precipitated as
MgNH4PO4 ×6H2O using (NH4)2HPO4 as the precipitant.

The precipitate’s solubility in neutral solutions (0.0065 g/100 mL

in pure water at 10 °C) is relatively high, but it is much less
soluble in the presence of dilute ammonia (0.0003 g/100 mL in
0.6 M NH3).

The precipitant is not very selective, so a preliminary separation

of Mg2+ from potential interferents is necessary. Calcium, which
is the most significant interferent, is usually removed by its prior
precipitation as the oxalate.

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Determination of Mg2+ in Water and Wastewater

The presence of excess ammonium salts from the precipitant or
the addition of too much ammonia can lead to the formation of
Mg(NH4)4(PO4)2, which is subsequently isolated as Mg(PO3)2
after drying.

The precipitate is isolated by filtration using a rinse solution of

dilute ammonia. After filtering, the precipitate is converted to
Mg2P2O7 and weighed.

Proper procedure for transferring the

supernatant to the filter paper cone.

Proper procedure for filtering solids using

filter paper. The filter paper circle in (a) is
folded in half (b), and folded in half again
(c). The filter paper is parted (d), and a small
corner is torn off (e). The filter paper is
opened up into a cone and placed in the Procedure for filtering through a filtering
funnel (f). Note that the torn corner is placed crucible. The trap is used to prevent water
to the outside. from a water aspirator from backwashing
into the suction flask.

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Procedure.
•Transfer a sample containing no more than 60 mg of
Mg2+ into a 600-mL beaker. Add 2–3 drops of methyl
red indicator, and, if necessary, adjust the volume to
150 mL.
Acidify the solution with 6 M HCl, and add 10 mL of
30% w/v (NH4)2HPO4. After cooling, add
concentrated NH3 dropwise, and while constantly
stirring, until the methyl red indicator turns yellow (pH
> 6.3).
After stirring for 5 min, add 5 mL of concentrated NH3,
and continue stirring for an additional 10 min.

•Allow the resulting solution and precipitate to

stand overnight.
•Isolate the precipitate by filtration, rinsing with 5%
v/v NH3.
•Dissolve the precipitate in 50 mL of 10% v/v HCl,
and precipitate a second time following the same
procedure.
•After filtering, carefully remove the filter paper by
charring. Heat the precipitate at 500 °C until the
residue is white, and then bring the precipitate to
constant weight at 1100 °C.

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Questions

1. Why does the procedure call for a sample containing no

more than 60 mg of Mg2+?

A sample containing 60 mg of Mg2+ will generate approx.,

600 mg, or 0.6 g, of MgNH4PO4 ×6H2O.

This is a substantial amount of precipitate to work with

during the filtration step. Large quantities of precipitate
may be difficult to filter and difficult to adequately rinse
free of impurities.

2. Why is the solution acidified with HCl before the

precipitant is added?

The HCl is added to ensure that MgNH4PO4 ×6H2O does not

ppt when the precipitant is initially added. Because PO4 3– is a
weak base, the precipitate is soluble in a strongly acidic
solution.

If the precipitant is added under neutral or basic conditions

(high RSS), the resulting ppt will consist of smaller, less pure
particles. Increasing the pH by adding base allows the ppt of
MgNH4PO4 ×6H2O to form under more favorable (low RSS)
conditions.

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3. Why is the acid–base indicator methyl red added to the

solution?
The indicator’s color change, which occurs at a pH of approx.
6.3, indicates when sufficient NH3 has been added to neutralize
the HCl added at the beginning of the procedure. The amount of
NH3 added is crucial to this procedure.

If insufficient NH3 is added, the ppt’s solubility increases,

leading to a negative determinate error. If too much NH3 is
added, the precipitate may contain traces of Mg(NH4)4(PO4)2,
which, on ignition, forms Mg(PO3)2.

This increases the mass of the ignited precipitate, giving a

positive determinate error. Once enough NH3 has been added
to neutralize the HCl, additional NH3 is added to quantitatively
precipitate MgNH4PO4 ×6H2O.

4. Explain why the formation of Mg(PO3)2 in place of

Mg2P2O7 increases the mass of precipitate.

The desired final precipitate, Mg2P2O7, contains two

moles of Mg, and the impurity, Mg(PO3)2, contains
only one mole of Mg.

Conservation of mass, therefore, requires that 2 moles

of Mg(PO3)2 must form in place of each mole of
Mg2P2O7. One mole of Mg2P2O7 weights 222.6 g.
Two moles of Mg(PO3)2 weigh 364.5 g.

Any replacement of Mg2P2O7 with Mg(PO3)2 must

increase the precipitate’s mass.

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5. What additional steps in the procedure, beyond those

discussed in questions 2 and 3, are taken to improve the
precipitate’s purity?

Two additional steps in the procedure help form a

precipitate that is free of impurities: digestion and
reprecipitation.

6. Why is the precipitate rinsed with a solution of 5% v/v

NH3?

This is done for the same reason that precipitation is

carried out in an ammonical solution; using dilute
ammonia minimizes solubility losses when rinsing the
precipitate.

An ore containing magnetite, Fe3O4, was analyzed by

dissolving a 1.5419-g sample in conc. HCl, giving a
mixture of Fe2+ 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.

SOLUTION

This is an example of a direct analysis since the iron in the

analyte, Fe3O4, is part of the isolated precipitate, Fe2O3.
Applying

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3 ´ moles Fe3O4 = 2 ´ moles Fe2O3

Using formula weights, FW, to convert from moles to grams in

the preceding equation

solved for grams of Fe3O4 and

%w/w Fe3O4 in the sample.

Limitations of Gravimetric Analysis

• Any interferents must
be removed prior to
precipitation
• Method is not very
sensitive

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Species Precipitated form Form weighed Some interfering

analyzed species
K+ KB(C6H5)4 NH4+, Ag+, Hg2+, Tl+, Rb+,
Cs+
Mg2+ Mg(NH4)PO4.6H2O Mg2P2O7 Many metals except Na+
and K+
Ca2+ CaC2O4.H2O CaCO3 or CaO Many metals except Mg2+,
Na+, or K+
Ba2+ BaSO4 BaSO4 Na+, K+, Li+, Ca2+, Al3+,
Cr3+, Fe3+, Sr2+, Pb2+,
NO3-
Ti4+ TiO(5,7-dibromo-8- same Fe3+, Zr4+, Cu2+, C2O42-,
hydroxyquinoline)2 citrate, HF
VO43- Hg3VO4 V2O5 Cl-, Br-, I-, SO42-, CrO42-,
AsO43-, PO43-
Cr3+ PbCrO4 Ag+, NH4+
Mn2+ Mn(NH4)PO4.H2O Mn2P2O7 Many metals
Fe3+ Fe(HCO2)3 Fe2O3 Many metals
Ni2+ Ni(dimethylglyoximate)2 same Pd2+, Pt2+, Bi3+, Au3+

Characteristics of Good Gravimetric

Techniques
• Ideally Precipitates in a gravimetric analysis should
be:
• Insoluble, Ksp should be way below the amount
expected in solution. Limiting factor for detection is
usually the balance, not Ksp. (For larger samples,
this may not be true.)
• Easily filterable, make large crystals which separate
from solution easily
• Pure with known composition, that is, they do not
make a whole bunch of insoluble complexes.

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Tips for good Gravimetric Analyses

• Things which can be done
for best gravimetric results:
• Cool solution after
precipitation has started.
• Add precipitating reagent
slowly so crystals are larger
• Keep the volume of solution
large so concentration of
analyte and precipitant is
low.

Summary of the 7 Steps in

Gravimetric Analysis
• Dry and weigh sample
• Dissolve sample
• Add precipitating reagent in excess
• Coagulate precipitate usually by heating
• Filtration-separate ppt from mother liquor
• Wash precipitate (peptization)
• Dry and weigh to constant weight

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Suction Filtration

• Filter flask
• Buchner funnel
• Filter paper
• Glass frit
• Filter adapter
• Heavy-walled rubber
tubing
• Water aspirator

Suction Filtration

• Mother liquor

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Advantages/Disadvantages
• Experimentally simple and elegant
• Accurate
• Precise (0.1-0.3 %)
• Macroscopic technique-requires at
least 10 mg ppt to collect and weigh
properly
• Time-consuming (1/2 day?)

Laboratory procedures
Transfer of solids
• Single chunk handle with
tweezers
• Powdered transfer washings with
at least 3 times with solvent
• Weighing bottles: tight fitting
ground glass joints prevents
contamination or loss of sample.
When handling ground glass
joints use either paper or tongs
• Handling precipitates Solution
is precipitated

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Laboratory Technique Considerations

1. Filters
– Paper is very hydroscopic, hard to get reliable tare weight
– GFF made from glass fibers less hydroscopic but should still be kept in
desicator. Very fine pores, different pore sizes available.
– Sintered glass fibers cannot be heated to high temperatures
2. Transferring
– decant: Pour majority of supernatant through without disturbing
precipitate.
– Wash precipitate: decant wash solution.
3. Control of moisture
• Moisture is ubiquitous in the laboratory, in order to control for
this a dry atmosphere will have to be maintained in a
reproducibly dry atmosphere by storage in a desicator or
evaporation or ignition

Laboratory Considerations continued

4. Drying: Occurs by putting an open weighing bottle (may be
covered with a watch glass) at a temperature slightly above
100oC to get rid of water or waters of hydration.
5. Weighing to constant weight means with +0.1mg
• Requires more than one weighing!!!
6. Desicators
• Objects cannot be weighed when hot or warm. But if you
were to take a sample out and wait for it to cool it would pick
up moisture like that so put it in a desicator. Don’t seal
descicator, creates a vacuum Desicant blue dry pink wet

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Common Desiccants
Mechanism of Action
Hydration ANHYDRONE®
(Magnesium Perchlorate
anhydrous), CaCl2,
MgO, MgSO4, K2CO3,
KOH, Drierite, Na2SO4
(anhydrous), H2SO4,
ZnCl2
Absorption and/ or BaO, CaSO4, Molecular
Adsorption Sieve, H3PO4, NaOH
Pellets
Chemisorption CaO, P2O5

• Silica gel goes from blue to • Anhydrous sodium sulfate

pink as it absorbs moisture gets clumpy as it absorbs
Can be regenerated in oven water

More Information about desiccants including common interferents and

regeneration temperature can be found at:
http://www.jtbaker.com/techlib/documents/3045.html

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Further laboratory considerations

7. Evaporating: Evaporating dishes allow rapid
evaporation but also are easy to tip otherwise
cause loss of analyte. Glass beads may be
added to avoid bumping and loss of analyte.
8) Ignition: Hotter temperature for elimination
of water or other reactant
• Muffle furnaces that go up to 1100oC are used
primarily for this Need to use porcelain
crucible.

Example
• A raw sewage sample was brought in for total
suspended solids and volatile solids analysis. A
portion of the sample was poured into a tared
evaporating dish and weighed. The sample was then
heated at 105oC for 4 hours, weighed, heated at
550oC overnight, and weighed again. The data are as
follows:
• Tare wt. 42.9073g
• Wet sample 104.4680g
• 105 wt. 45.4140g
• 550 wt. 43.3236g
• What is the TSS in g/L? What percent of the
solids are volatile?

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Why are we concerned about solubility

considerations when doing gravimetric analysis?
• Precipitate must be insoluble so that
greater than 99.99% of analyte present in
solution precipitates in order for
gravimetric analysis to be considered
quantitative
• Solubility losses (to solution) can be
minimized by carefully controlling the
composition of the solution in which the
precipitate forms. This requires
understanding the relevant equilibrium
reactions affecting the precipitates
solubility.

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