Gravimetric Analysis and

Precipitation Equilibria
Dr. A.K.M. Shafiqul Islam
&
Dr. Zarina Zakaria
 Introduction
 The term gravimetric pertains to a Weight
Measurement.
 Gravimetric method is one in which the analysis
is completed by a weighing operation.
 Gravimetric Analysis is a group of analytical
methods in which the amount of analyte is
determined by the measurement of the mass of
a pure substance containing the analyte.
 Gravimetric Methods can also be defined as
quantitative methods based on the determining
the mass of a pure compound to which the
analyte is chemically related.
There are two main types of gravimetric analyses

A) Precipitation
A chemical reaction causes the formation of a sparingly soluble
substance that precipitates from solution is filtered, washed,
purified (if necessary) and weighed.

B) Volatilisation
In this method the analyte or its decomposition products are
volatilised and then collected and weighed, or alternatively,
the mass of the volatilised product is determined indirectly
by the loss of mass of the sample.
 Example for Precipitation:-

 Calcium can be determined gravimetrically by

precipitation of calcium oxalate and ignition of
the oxalate ion to calcium oxide.

 Ca2+ + C2O42- →CaC2O4

 CaC2O4 → CaO + CO2 + CO

 The precipitate thus obtained are weighed and

the mass of calcium oxide is determined.
 Example for Volatilisation:-
The analyte or its decomposition products are volatilised at
a suitable temperature. The volatile product is then
collected and weighed, i.e. the mass of the product is
indirectly determined from the loss in mass of the sample.

Example
Water can be separated from most inorganic compounds by
ignition, the evolved water can then be absorbed on any
one of several solid desiccants. The weight of water
evolved may be calculated from the gain in weight of the
absorbent.
Not all insoluble precipitates are well suited for gravimetric
analysis.

It is important to consider what properties are required in order

that a precipitate be applicable for a quantitative precipitation
method:-

Solubility

Filterability

Chemical Composition

Other Desirable Properties

 Solubility
The product must be sufficiently insoluble to prevent the loss of
weight.

Filterability

Precipitate formed should be adoptable to simple and rapid

filteration methods.

Chemical Composition

The product must be of known chemical composition.

Other Desirable Properties

Other factors effecting the stability and purity of the precipitate.

For a successful determination in gravimetric analysis the
following criteria should be met :-

(1)The desired substance must be completely precipitated. In

most determination the precipitate is of such low solubility
that losses from dissolution are negligible. An additional
factor is the common ion effect, this further decrease the
solubility of the precipitate.

E.g. When Ag+ is precipitated out by addition of Cl-

Ag+ + Cl- = AgCl

The low solubility of AgCl is reduced further by the excess

of Cl- which is added force to the reaction to proceed
towards right side.
For a successful determination in gravimetric analysis the
following criteria should be met :-

(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 which is pure or which is free
from impurities. This could be reduced by careful
precipitation and sufficient washing.
 Gravimetric Analysis
 Gravimetric analysis is potentially more accurate
and more precise than volumetric analysis.
 Gravimetric analysis avoids problems with
temperature fluctuations, calibration errors, and other
problems associated with volumetric analysis.
 But there are potential problems with gravimetric
analysis that must be avoided to get good results.
 Proper lab technique is critical
 Steps in a Gravimetric Analysis
1. Preparation of the solution
2. Precipitation
3. Digestion
4. Filtration
5. Washing
6. Drying or ignition
7. Weighing
8. Calculation
1. Preparation of analyte solution
 Gravimetric analysis usually involves
precipitation of analyte from solution.

 May need to separate potential interferences

before precipitating analyte

 May require pH and/or other adjustments to

maximize precipitate formation

 When possible, select precipitating agents

that are selective (or specific, if possible).
2. Precipitation
 The precipitate should
 Be insoluble, but not too insoluble
 Have large crystals
 Easier to filter large crystals
 Be free of contaminants
 The smaller the surface area the better

 The smaller the solubility, S, the greater the tendency to

form lots of small crystals that trap contaminants and
are difficult to filter

 The greater the solubility, the more analyte is left

unprecipitated
 We need to strike a balance
 (but not the analytical balance, please)
 The von Weimarn Ratio
 von Weimarn ratio = (Q – S)/S

 A measure of relative supersaturation

 The lower the better
 If high, get excessive nucleation, lots of small crystals, large surface
area
 If low, get larger, fewer crystals, small surface area
 Q = concentration of mixed reactants before precipitation
 Keep it low by using dilute solutions, stir mixture well, add reactants
slowly
 S = solubility of precipitate at equilibrium
 Keep it high with high temperatures, adjusting pH
 Can lower S later by cooling mixture after crystals have formed
 Digestion of the Precipitate
 Very small crystal with a large specific surface
area have a higher surface energy and a higher
apparent solubility than large crystals. This is an
initial rate phenomenon and does not represent
the equilibrium condition, and it is one
consequence of heterogeneous equilibria. When
the precipitate is allowed to stand in the
presence of mother liquor (the solution from
which it was precipitated), the larger crystal
grow at the expanse of the small ones. This
process is called digestion, or Ostwald
ripening. The small particles tend to dissolve
and precipitate on the surfaces of the larger
crystals
 Digestion of Crystalline
Precipitates –(1)
When a crystalline precipitate is allowed to stand in contact with
the solution from which it was precipitated (mother liquor), it is
more easily filtered and requires a less dense filtering medium
than the freshly formed precipitate.

This improvement in filterability is accelarated by heating,

common practice is to treat crystalline precipitates in this
manner prior to filtration. The process is called DIGESTION.

Considerable experimental evidence indicates that the digestion

process consists of a cementing together of crystals. The resulting
aggregates are appreciably larger than the individual crystals
and are therefore more easily retained.
 Digestion of Crystalline
Precipitates –(2)
Ions making up a precipitate are in dynamic equilibrium with
their counterparts in the solution. As a result, solution and
reprecipitation of the solid take place constantly.

The latter process can occur in such a way as to form bridges

between adjacent solid particles thus leading to crystalline
aggregates.
At elevated temperatures, where the solubility is
greater, the process would be expected to take place at an
accelerated rate, this is in keeping with the experimental
observation that the effectiveness of digestion is greater at
higher temperatures.
 Digestion of Crystalline
Precipitates –(3)
The improved filterability of precipitates after digestion has
also been attributed wholly or in part to growth of large
crystals at the expense of small ones. Such process might
occur since theoretically small crystals should be more
soluble than large ones.

Therefore, digestion of a mixture of crystals results in the

disappearance of the more soluble smaller particles and
growth of the larger and more insoluble ones.

There was however some experimental evidence that the very

smallest crystals of the solid may have disappeared during
the digestion.
 Impurities in Precipitation
 Precipitates tend to carry down from the
solution constituents that are not normally
soluble, causing the precipitate to become
contaminated. This process is called co-
precipitation.
 Co-precipitation
At least four types of co-precipitation can be
recognized
a. Occlusion and Inclusion
b. Surface Adsorption
c. Isomorphous Replacement
d. Postprecipitation
 a. Occlusion and Inclusion
Occlusion is a type of coprecipitation in which the soluble
impurity is enclosed or entrapped within the crystal
structure of the solid. As such it acts as a seat of
imperfection within the crystal.

Generally, occluded substances are distributed in a non

homogeneous fashion throughout the crystal.

In addition, the amount of occluded substance is greatly

influenced by the conditions and manner of precipitate
formation.
 a. Occlusion and Inclusion

Inclusion occurs when ions, generally of large size or

charge, are trapped within the crystal lattice
(isomorphorous inclusion, as with K+ in NH4MgPO4
precipitation)

Occlusion and inclusion impurities are difficult to remove.

Digestion is effective in reducing the quantity of entrapped
contaminant.
 b. Surface Adsorption
 All precipitates carry down soluble impurities by adsorption
on their surfaces.

 However, only where the specific surface areas are great does
coprecipitation of this type have an appreciable effect on the
weight of the solid.

 Therefore contamination by surface adsorption will be

important only when dealing with colloidal precipitates.

 Colloidal particles formed under analytical conditions will

always have adsorbed on their surfaces one of the constituent
ions of the precipitate.
 b. Surface Adsorption
 Let’s use AgCl as an example

 Primary adsorption layer

 Ion in excess adsorbs on the surface of the precipitate
 Crystal becomes positive if Ag+ is in excess
 Crystal becomes negative if Cl- is in excess

 Counter-ion layer (counterlayer)

 Charged crystal attracts ions of opposite charge
 For example, NO3- attracted to positive crystal, results in a layer of
silver nitrate around the AgCl
 For example, Na+ attracted to negative crystal, results in a layer of
NaCl around the AgCl
 The more dilute the solution, the thicker is the counter-ion layer
 Colloidal Precipitates (Such as
AgCl
 When S is very small (very insoluble
precipitates), cannot avoid high degree of
nucleation and very small crystals
 Colloidal particles 1 to 100 μm in diameter
 Surface area as high as 3,000 ft2/g
 High potential for surface adsorption
 Other problems besides surface adsorption
 Colloidal precipitates cause difficulties in filtering and
washing as well
Colloidal Particle in Solution
Positively charged primary adsorption
layer on colloidal particle

NO3−
NO3− H+
H+ NO3−
NO3−
Ag+ Cl− Ag+ Cl− Ag+ Cl− Ag+
NO3−
Ag+ Cl− Ag+ Cl− Ag+ Cl− Ag+

NO3− Ag+ Cl− Ag+ Cl− Ag+ Cl− Ag+

NO3−
Cl− Ag+ Cl− Ag+ Cl− Ag+
NO3−
H+ Ag+ Ag+
NO3−
H+
− Counter-ion
NO3
layer of solution
with excess anions Ag+

Colloidal solid
Homogeneous solution
(charges balanced)

Coagulation: aggregation of colloidal particles into larger filterable masses

 b. Surface Adsorption

 Several techniques are adopted to reduce the

magnitude of error arising from adsorption of
contaminants on a colloidal precipitate.

 Among these are the use of elevated temperatures

and dilute solutions, digestion, washing and
reprecipitation.
 c. Isomorphous Replacement
 Two compound are said to be isomorphous if they have
the same type of formula and crystallize in similar
geometric forms. When their lattice dimension are about
same, one ion can replace another in a crystal, a
resulting in a mixed crystal. This process is called
isomorphous replacement.

 For example, in the precipitation of Mg+2 as magnesium

ammonium phosphate, K+ has nearly the same ionic size
as NH4+ and can be replaces it to form magnesium
potassium phosphate.

 Isomorphous replacement is very serious and very little

can be done about it.
 d. Post Precipitation

A type of contamination wherein the impurity is an

insoluble compound that precipitates after all or a major
part of the analytical precipitate has formed.

 Post precipitation arises only when the attempt is made to

separate two ions on the basis of the rate at which they
precipitate.

 This will come down if the solution is allowed to stand too

long before being filtered.
3. Digestion (Ostwald Ripening)
 Let precipitate stand in contact with solution,
usually at high temperature
 Large crystals (small surface area) have lower
free energy than small crystals (large surface
area)
 Digestion makes larger crystals, reduces surface
contamination, reduces crystal imperfections
 Digestion coagulates a colloid (causes the particles to
agglomerate, or stick together), but surface area does
not decrease as much as if larger crystals actually
grew
 Hydrophilic vs. Hydrophobic
Colloids
 Hydrophilic (water-loving) colloids form gels and
do not coagulate well
 Hydroxides (Al(OH)3, Fe(OH)3, for example) often
form gels and are very difficult to filter
 Hydrophobic (water-fearing) colloids coagulate
readily
 Luckily, AgCl is hydrophobic
 Gravimetric analysis of silver or chloride by AgCl
precipitation is effective in spite of colloidal nature of
precipitate
 4. Filtration
 Sintered glass crucibles are used to filter the
precipitates. These are marked as fine, medium and
coarse porosities (marked f, m and c).

 The crucibles first cleaned thoroughly and then

subjected to the same regimen of heating and cooling as
that required for the precipitate. This process is repeated
until constant mass has been achieved, that is, until
consecutive weighings differ by 0.3 mg or less.

 Colloidal precipitates present filtering problems if

particles are too small
 Can plug filter paper or glass or pass right through the filter if
not coagulated well
 Hydrophobic colloids generally filter better than hydrophilic
colloids
 5. Washing
 Removes the mother liquor
 May also remove some of the coprecipitated
compounds
 Can cause peptization of colloids
 Diluting the counter-ion layer causes it to get larger,
forcing coagulated colloidal particles apart
 And THERE THEY GO right through the filter
 Wash with a solution of a volatile electrolyte that will
be removed in drying step
 6. Drying or Igniting
 Dry the precipitate to remove water and volatile
electrolytes from wash solution

 Ignition (very high-temperature drying) converts

precipitates to compounds more suitable for
weighing
 Removes water of hydration
 Converts hygroscopic compound to non-hygroscopic
compound
e.g., MgNH4PO4 is decomposed to the
pyrophosphate Mg2P2O7 by heating at 900 oC
 Sometimes it even converts the filter paper to ash
 Obtaining a Final Known
Composition
 Ignition is often used to drive off water or give
an oxide form
850o C 1hr
Fe(HCO )  H 2O(s) 
-
2 3 Fe2O3 (s)  CO2(g)  H 2O(g)

 Thermogravimetry is a form of gravimetric

analysis where mass is measured as a function of
temperature:
OH
O
CO 2 CO2
Ca
300o C
Ca
 500o C 700o C
 CaCO3  CaO
O
HO

O
Thermogravimetry
 Combustion Analysis

Absorbs Absorbs
water CO2

Find the empirical formula for a 13.72 mg organic

sample that produced 6.97 mg of water and 28.44
mg of carbon dioxide
 7. Weighing
 Properly calibrated analytical balance
 Good weighing technique
 Avoid static electricity
 Review important points on p. 51
periodically
 And now, step 8, the calculations
 Chem 105 stoichiometry, anyone?
 Organic Precipitates
 Organic precipitating agents have the advantages of
giving precipitates with very solubility in water and a
favorable gravimetric factor.

 Most of them are chelating agents that forms slightly

insoluble, uncharged chelates with the metal ions.
Organic Precipitates
 Gravimetric Analysis: Weight
Relationship

From the weight of the precipitate formed in a gravimetric

analysis, we can calculate the weight of the analyte from the
weight relationship of the precipitate and analyte.

The weight of the analyte is calculated from the weight of the

precipitate.
E.g. If we consider calculating the percentage of Cl2 by weighing
the AgCl precipitate, then

Cl2--------> 2AgCl (we get 2 moles of AgCl from 1 mol Cl2)

Calculation of the corresponding weight of Cl2 that would be

contained in the AgCl sample will be:-

gm Cl2 / gm AgCl = [F. Wt. Cl2 ] / [F. Wt. AgCl

x [1 mol Cl2 / 2 mol AgCl]

 gm Cl2 = [gm AgCl] x [70.906 gm Cl2 / 1 mol Cl2] x

[1 mol AgCl / 143.32 gm AgCl] x
[1 mol Cl2 / 2 mol AgCl]
We can consider Gravimetric Factor (GF) as: -

f wt. analyte (g/mol) a

GF  x (mol analyte/mo l precipitat e)
f wt. precipitat e (g/mol) b

Then,

gm Cl2 = gm AgCl x GF(gm Cl2/gm AgCl)

GF = f. wt. of substance sought / f. wt. of substance weighed

x a/b (mol sought / mole weighed)
#1 A 0.3516 gm 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 P to H3PO4. The phosphate was
precipitated with Mg2+ followed by aqueous NH3 to form
MgNH4PO4.6H2O. After being filtered and washed, the precipitate was
converted to Mg2P2O7 (FW=222.57) by ignition at 1000º C. This residue
weighed 0.2161 gm. Calculate the percent P (FW = 30.974) in the
sample.

Gravimetric factor, GF = f. wt. of substance sought / f. wt. of substance

substance weighed x a/b (mol sought / mol weighed)

GF = 30.974 gm / 222.57 gm x 2/1 = 0.278

Amount of P = GF (0.278) x Wt. of precipitate (0.2161) = 0.0601gm

 % P = 0.0601 gm P / 0.3516 gm sample x 100 = 17.11%

#2 A 0.4960 gm sample of a CaCO3 is dissolved in an acidic
solution. The calcium is precipitated as CaC2O4.H2O and the
dry precipitate is found to weight 0.6186 gm. What is the
percentage of CaO in the sample? (FW CaO = 56.08; FW
CaC2O4.H2O = 146.2)

GF = 56.08 gm / 146.12 gm X 1/1 = 0.3838

Wt of CaO = Wt. of ppt. X GF = 0.6186 gm X 0.3838

= 0.2374 gm

% of CaO in CaCO3 = 0.2347 gm / 0.4960 gm x 100

= 47.87%
 Precipitation Reactions
 Two fully dissolved and dissociated
compounds are mixed and a “precipitate”
(solid product) forms
 The mixture becomes opaque due to the
formation of solid
 Precipitation Reactions

 Barium Iodate in Water:

Ba(IO3)2(s) Ba2+(aq) + 2 IO3(aq)
saturated solution contains excess solid

 At Equilibrium:
Ksp = [Ba2+][IO3−]2

 Solubility Product (in general):

for salt MxAy: Ksp = [M]x[A]y
Precipitation Reactions
How many grams of Ba(IO3)2 dissolve in 500 mL of water
At 25 C if Ksp = 1.57 × 10−9

Ba(IO3)2(s) Ba2+(aq) + 2 IO3(aq)

S S 2S

Ksp = [Ba2+][IO3−]2 = [S][2S]2 = 1.57 × 10−9

4S3 = 1.57 × 10−9

S (molar solubility of Ba(IO3)2) = 7.32 x 10−4 mol L−1

You must learn how to use your calculator!

Precipitation Reactions
How many grams of Ba(IO3)2 dissolve in 500 mL of water
At 25 C if Ksp = 1.57 × 10−9

S = 7.32 × 10−4

mmol Ba(IO3)2 = S × Vml = (7.32 × 10−4)(500 mL) = 0.366 mmol

Wt. Ba(IO3)2 = 0.366 mmol × 487 mg mmol−1 = 178 mg  0.178 g

This could cause a significant error in a gravimetric analysis

 Common Ion Effect
The presence in solution of an excess of one ion from a
slightly soluble ionic substance depresses its solubility
(more complete precipitation).
How many grams of Ba(IO3)2 dissolve in 500 mL of 0.0200
M Ba(NO3)2 at 25 C if Ksp = 1.57 × 10−9

Ba(IO3)2(s) Ba2+(aq) + 2 IO3(aq)

S S + 0.0200 2S

[Ba2+][IO3−]2 = (S + 0.0200)(2S)2 = 1.57 × 10−9

Assumption: S << 0.0200 M

(0.0200)(2S)2 = 1.57 × 10−9  S = 1.40 × 10−4 M

Wt. Ba(IO3)2 = 1.40 × 10−4 M × 500 mL × 487 mg mmol−1 = 34.0 mg

 Theory of Precipitation
 Precipitation occurs when the ion product
exceeds the solubility product

For MxAy: CMx × CAy > Ksp

 Two Steps in Precipitation

 Nucleation: small groups of ions form stable

solid masses (nuclei)

 Particle Growth: ions from solution add on to

nuclei to form particles
 Theory of Precipitation
 The amount by which the ion product exceeds the
solubility product is expressed qualitatively as
supersaturation.

Supersaturation = Q − S
Q: instantaneous concentration

S: equilibrium concentration (molar solubility)

 Large supersaturation favors nucleation

 Small supersaturation favors particle growth

 Minimizing Supersaturation
Supersaturation = Q − S

1. Elevated Temperature (increase S)

2. Dilute Solution (decrease Q)
3. Slow Addition, good stirring (decrease Q)
 TUTORIAL
 Read Gary text book on 314 to 320 and
understand the topics. Extract the
objective/purpose of steps in gravimetrics
analysis.
 Do questions number 16, 22, 27 and 32
complete with the calculations.