CHAPTER

2 Results of coin flipping

Gravimetric Method of Analysis

 Syllabus
Topics to be Covered
1.  Introduction
2.  Gravimetric calculation, Chemical Stoichiometry
3.  Properties of precipitates and precipitating agents (formation of
precipitates)
4.  Drying and ignition of precipitates
5  Organic precipitants
6.  Applications of gravimetric methods
 Introduction:

• An analytical method based on measurement of mass.

• No Standardization and Calibration is required.
• In few cases it may be highly accurate than the
modern Instrumental Methods.

Principle:
Analyte is physically and
chemically separated (from
solvent and impurities)
→ Purified product
(with constant weight).
For gravimetric analysis
the precipitate should be pure
and filterable.
 Types
Precipitation Gravimetry:
Precipitation from the solution by adding two reagents: Where, IP > SP,
Analyte + reagent →sparingly soluble precipitate/ complex….
Ca2+ + C2O42- (excess) A m m o nia CaC2O4(ppt.)  CaO + CO2 + CO
Gravimetry by Crystallization:
If supersaturated solution is cooled, to carry crystallization.
Volatilization Gravimetry:
Analyte → Volatilized mass or decreased mass is calculated.
Determination of sodium hydrogen carbonate in antacid tablet;
NaHCO3 + H 2SO4 CO 2 + H 2O (l) + NaHSO4 (aq)
NaOH Na2CO3

difference in mass gives the CO2

Electrogravimetry:
Different precipitates (commonly metals) are precipitated on the electrode
surface.
Gravimetric Titrimetry:
The mass of a standard reagent required to react completely with the analyte
provides the information needed to determine the analyte concentration.
Principle: Gravimetric calculations
General principle of aA rR AaRr
gravimetry: Analyte Reagent Product
x gm y gm
• It is based on the
chemical stoichiometry. From the law of conservation of moles,

• The weight of product Moles of analyte in sample = a X moles of precipitates

gives the amount of or, x/MA = a X y/MP
analyte. MA
or, x = aX Xy
• Process or reaction MP
should be complete. GF
• Substance weighed In General, aA + R bP
should have the definite a moles b moles

composition. a X MA Coeff. of analyte X MW analyte

• Determination of G.F. =
b X MP = Coeff. of product X MW product
gravimmetric factor (GF)
a X gfw substance sought
makes the calculation =
b X gfw substance Weighed
easy.
Solvent extraction, Chromatography, Distillation types of methods can also be used for
the separation of the analyte. This type of analysis is mostly carried prior to
precipitation.
Gravimetric factor (GF)
How do you interpret?
The number of gm of analyte present in 1 gm of the product of known composition.
It is constant for a reaction, which when multiplied by mass of product the mass of analyte
can be obtained.
Mass of analyte = GF × Mass of product
An example:
• Determination of i) % Fe and ii) % Fe3O4in an iron ore
[A/MWt: (Fe = 55.847, Fe2O3 = 231.54, Fe3O4 = 303.387)]
0.4852 gm dissolved in conc. HCl 2+ 3+ boiled with HNO3 3+
1 gm magnetite Fe , Fe all to Fe

0.2481gmignited to high temperature precipitated

0.5394 gmFe2 O3 Fe2 O3 .xH2 O
by NH3
2 M Fe Fe = 55.847
(i) GF    0.6994
1 M Fe2O3
Fe2O3 = 231.54
2 M Fe3O 4 Fe3O4 = 303.387
(ii) GF    0.9662
3 M Fe2O3

Wt. A  Wt. P  GF
Finally use relation
weight of P  GF
%A  100%
weight of sample
 Try these problems
AWt./MWt.: AgCl=143.32, Cl=35.5, Na2C2O4 =134.0, CO= 28.01, Fe2O3 = 231.54 ,
P 2O5 = 141.95, Mg2 P2O7 = 222.55, P = 30.974

• 0.7203g Cl-salt is precipitated as AgCl, to be 0.4026 g calculate the % of Cl in the

sample. % expressed as NaCl.
• At an elevated temperature Na2C2O4 is converted to Na2CO3 with the evolution of
CO. Ignition of1.906 gm impure sampe yield the residue that weighed 0.9859gm.
Calculate the percentage purity of the sample.
• Calculate the number of mL of ammonia, density 0.99g/mL, 2.3% by weight of
NH3, which will be required to precipitate as Fe(OH)3 the iron in 0.70 g sample
that contain 25% Fe2O3. [4.9mL]
• What size sample containing 12.0% chlorine (Cl) should be taken for analysis if
the chemist wishes to obtain a precipitate of AgCl which weights 0.500g? [1.03g]
• 0.5428g phosphate rock is precipitated as MgNH 4PO4.6H2O and ignited to
Mg2P2O7. The ignited ppt weights 0.2234g calculate, (a) % of P 2O5 in the sample
(b) % purity expressed as P rather than P2O5.,
Ans, 26.25%, 11.46%
 Properties of precipitates and precipitating agents, for the gravimetric
analysis

The ideal precipitate An ideal precipitating agent

• Possess a sufficiently low
solubility (no loss while washing). • Should be specific (DMG
• Readily filterable, large particle for Ni) or at least selective
size, washable to remove
(AgCl for halides). i. e.
impurities.
should react with only
• The precipitate must be large
one analyte….
enough to settle out of solution
• Feasible for filtration • Large MW.
• Inert to atmosphere and the • Available.
environment (must be stable). • High stability.
• Pure with known composition
after drying and ignition.
Add more: if required The precipitation process must be complete.
 There are two methods of precipitations
1. Nucleation:
• Process where ions or dissolved particles
instantaneously combine to give precipitate in
the solution.
• It is the the initial step of precipitation; if IP >
SP:
• It is considered to be the most difficult step.
Why???
• Precipitate of infinitesimal size are formed.
• This process is feasible in any part of the
solution (bulk process).
• If there is only nucleation small sized colloidal
or gelateneous ppts will be formed. These
kinds of precipitates are difficult to be handled
The relative rate of these two processes determines the particle size. As the size increases to
10-4 , only after that it will start to pulled down by gravity and so will be settled down]
2. Crystal growth
• It is the process where ions or
dissolved particles collide with the
previous precipitate and get
attached there by increasing the
size of precipitate.
• Occurs only on the surface of
previous crystal..
• Produce large size of precipitates,
which are easy to handle, so It is more
favored process for gravimetric
determination.
• Some impurities may be entrapped in
this process.
• High rate of particle growth gives large
sized ppts

Ions mostly passes through the colloidal state to generate the precipitates.
 Control over the particle size:

• Von-Weimarn Principle:
• He studied the co-relation between concentration of reagent and the rate of
precipitation. The control over these factors will determines the size of precipitate.
• Relative supersaturation term, defined by, QS
RS 
S
Large RS fast nucleationlarge number
of small sized precipitates. • Q = Concentration of solute or ions at any
Small RS nucleation is slow  few but instant,
• S = Equilibrium solubility at that temperature
large sized precipitates.
(represents the force resisting the pptn/ large
S favors dissolvation).
• Q - S = Degree of supersaturation
• Thus “The initial rate of precipitation is proportional to
relative supersaturation”
• Controlling the terms Q and S, we can direct RS towards the
small quantity.
• Von-Weimarns theory is helpful for adjusting the
experimental conditions to obtain large precipitates.
• Change of temperature, concentration , rate of mixing,
stirring, controlling acidity if solubility depends on pH.

S Q  degree of relative supersaturation 

 Controlling Particle Size ( Optimal experimental conditions)

For crystalline precipitates :

• Use of elevated temperatures to
increase the solubility (S) of the
precipitate. Precipitation from hot solution.
The solubility of precipitates increases with The effect of relative supersaturation
temperature, (S). on the particle sizes of precipitate

• pH control, provided the solubility of the precipitate depends on pH.

• Use of complexing agents
• After the precipitate was formed, the particle size can be improved by
digestion process.

• Use of dilute solutions to minimize initial concentration (Q),

• Slow addition of the precipitating agent with good stirring,
minimize local Q at some specific positions. prevents local excesses of the
reagent
• By precipitation from homogeneous solution.
• Reprecipitation
• increasing solubility (S):
- Increase of temperature
precipitation are quite commonly carried out at elevated temperature.
• Changing pH: pH (e.g. salt of weak acids CaC 2O4 , ZnS are better
precipitated in acidic medium; BaSO4 is better precipitated at 0.01-
0.05M HCl, since the solubility is increased by formation of
bisulphate ion).
• On the other hand Fe(OH)3 It is a gelatinous precipitate cannot be
precipitated even in acidic medium, RS will still be large and produce
gelatinous mass. Are better ppted by homogeneous generation.
• Decreasing Q: Using dilute solution and adding precipitating
reagent at slow rate will moderately decreases the Q.
 Colloidal particles:
Dimensions (10-7-10-4cm)
Electrically charged
Cannot be filter (i) will penetrate (ii) do not settle by gravity
Precipitates having very low solubility's such as many sulfides and hydrous oxides generally forms
colloids.
Coagulaion of colloids:
• The process with which the colloidal particles are brought together so that they will
settle and can be separated by filtration is termed as coagulation.
• In solution Colloids are stable: *possess positive or negative charges on surface.
*same charge will undergo repulsion. *small particle has large surface/mass ratio; so
effectively adsorbs the ions.
• Peneth Fajan's Hahn rule: Lattice ions are preferentially adsorbed over other and if
no common lattice ion is present, the ion which form least soluble compound with
one of the lattice ion is most strongly adsorbed.
• For example, consider AgCl undergoing precipitation by addition of AgNO3 drops on
NaCl solution. The colloidal particle of AgCl thus formed will bear large numbers of,
Cl- ions on its surface. The solution will thus contain other iona Na+ NO3- … in excess.
the adsorbed Cl- ion (common ion) which is excess in the solution generates net
negative charge on the colloidal particle. Thus AgCl remains dispersed in solution as
colloidal precipitates.
 Colldals of AgCl in excess Cl- in excess AgNO3

-
Na
+ Na
+
Diffused Layer NO 3 -
- NO 3
+ NO 3 +
Na Cl- Na
+
Ag Ag+ -
- - NO 3
Cl Cl - Ag
+

+ NO 3 + +
Na Ag Ag
+ Cl- AgCl Cl- Ag
+ AgCl -
Na Cl-
- + NO 3
-
Cl -
Ag
Cl NO 3 +
Cl- Compact Layer Ag +
-
Ag -
+
Cl Na NO 3 Ag
+
+ Cl- -

Na NO 3

The surface of AgCl is The surface of AgCl

negatively charged is positively charged

• Presence of charge on colloidal particle favors the electrical double layer {inner
is primary (compact) and outer is secondary (diffused)}
• The charge on the surface is minimum then no ion is in excess in supernatant
liquid, in this state coagulation could occurs.
• Net charge on the surface of colloid concentrations of excess ion in solution
• As discussed, the magnitude of charge on the Ag+Cl- particle is determined by
the concentration of the common ion. The variation of effective charge on
concentration of ion on supernatant liquid will determine the distance of
closest approach between two neighboring particles. Look figure:
 Higher [Ag+] PPT lies far
from each other.

Lower [Ag+] PPT

lies more close
from each other.
Adding electrolyte could
have the same effect.

Fig: Effect of AgNO3 and electrolyte concentration on the thickness of double layer
surrounding a colloidal AgCl particle in a solution containing excess AgNO3.
• Nature of graph: The high effective charge at the surface of AgCl particle
decrease rapidly and becomes zero at d1, d2, d3. (charge is neutralized by
counter ions from secondary adsorbed layer).
• At low concentration of AgNO3; AgCl comes closer as compared to high
concentration.
• Increasing concentration of other electrolyte (or adding) reduces the
interaction between two similarly charged particles.
• Short period heating , stirring, (number of adsorbed ions decreases), thus
particles moves closer and can be coagulated.
 Peptization:
• It is the process for the formation of stable
dispersion of colloidal particles in water. It is
opposite of agglomeration.
• When Coagulation is carried by the addition
of foreign ion, during washing (a second
important part of gravimetric analysis for
removing impurities), these ions which had
decreased the repulsive force are lost and
peptization occurs.
• It is an undesirable process for gravimetry;
puts in dilemma about washing.

• This risk can be minimized by using volatile electrolyte while

washing, which still prevents the peptization. I can be easily removed
in drying and ignition process. For e.g. it is better to wash AgCl with
aqueous HNO3 solution. In some cases HCl could be volatile solvent.
 Digestion:
• After the precipitation is complete, before filtration;
precipitate is heated for an hour or more in the
solution from which it was formed (mother liquor), Mother

this is called digestion. liquor

• Digestion helps to improve filterability and purity of ppt

precipitates.
• Here particle size increases by Ostwald’s Ripening. DT

• Applicable only for the crystalline precipitates like

BaSO4, CaC2O4 etc
• At high T small particles are more soluble than the large one get dissolved.
• As an effect, solution becomes supersaturated for large particles.
• To maintain equilibrium ion will deposits on the surface of the large
particles and increase particle size further more. BaSO4
• Dissolution and re crystallization occurs continuously, i.e. large
particle grow in expense of small one thus called Ostwalds Ripening.
• Stirring will obstruct the improvement in filterability characteristics.
• Curdy ppt (AgCl), gelatinous ppt (Fe(OH)3) are not digested , are so insoluble that their
solubility doesnot increase appreciably at elevated temperature or the small particle
 Precipitate Types
Lyophilic Lyophobic
• Some colloids when coagulated • During coagulation very less solvent
retains large amount of water-jelly retained-suspensoids, lyophobic.
like ppt- gels or hydrogels. Emulsoids • Eg-AgCl
or lyophilic. Hydophilic coagulated colloids.
• Eg-Fe(OH)3 ,Al(OH)3,silicic acid

Crystalline Precipitates

Crystalline in nature
Easily filtered and purified
Precipitate often be improved significantly
controlling Q, and S.or both.
.
 Coprecipitation (Impurities in precipitate)
Unwanted substances can be precipitate together or carried down together with
precipitate during precipitation, the process is called coprecipitation.
i) surface adsorption,
Impurity get adsorbed on the surface. iii) occlusion
Large specific surface areas favors.
Carry down impurity which otherwise is When a crystal growth is rapid during
soluble. NO3- on AgNO3 precipitate formation, foreign ions or
Fe(OH)3 and Al(OH)3 bears charge which is counter ions in the counter-ion layer,
function of pH. Thus anions tend to be could not get time to escape and may
coprecipitated at low pH, cations at high pH. become trapped, or occluded, within
the growing crystal.
ii) mixed-crystal formation, iv) mechanical entrapment
Two types of compound, different in one
ion (with same charge and size (less than Mechanical entrapment occurs when
5% different)). crystals lie close together during
Same crystal structure, MgKPO4, in growth. Here, several crystals grow
MgNH4PO4, SrSO4 in BaSO4, MnS in CdS. together and in so doing trap a portion
BaSO4 and PbSO4 of the solution in a tiny pocket.

Surface adsorption and mixed crystal formation are equilibrium processes, whereas
occlusion and mechanical entrapment arise from the kinetics of crystal growth
 2) Mixed-crystal formation:
1) Surface adsorption
Excess
lattice ion get
adsorbed

Minimization: Minimization:
• Washing (mostly with electrolyte) • Separation of the interfering agent.
• Controlling pH • Using different precipitating reagent.
• Reprecipitation • Reprecipitation

3) occlusions : 4) Mechanical entrapment

Impurities are trapped in

pockets inside the growing
crystal
Minimization for (3)and 4)):
Using dilute and warm solutions
Lowering relative supersaturation.
for precipitation
e Digestion or Aging
Reprecipitation
 Minimizing Coprecipitation

 Method of addition of two reagents

 Washing
 Digestion
 Reprecipitaion
 Separation
 Precipitation from Homogenous Solution
• Homogenous precipitation is a process in which a
ppt is formed by slow generation of a
precipitating reagent homogenously throughout
a solution.
• Solids formed by homogenous precipitation are
generally purer and more easily filtered than ppt
generated by direct addition of a reagent to the
analyte solution Aluminum hydroxide formed by
• Relative supersaturation kept low. the direct addition of ammonia
(left), and the homogeneous
Ex. ppt of ferric formate by using urea and formic acid production of hydroxide (right).
NH2CONH2 + 3H2O  CO2 + 2NH4+ + 2OH–
OH– + HCOOH  HCOO– + H2O
3HCOO– + Fe3+  Fe(HCOO)3. nH2O
Direct addition
Hydrous oxides of Fe(III), As(III) of base Bulky and gelatinous
Are contaminated and
homogeneous difficult to filter
-
precipitation with OH

Prevents the condition with local high Dense, easily filtered and
concentration of reagent pure precipitates
 Postprecipitation
 The process by which an impurity is deposited after precipitation of the
desired substance is called postprecipitation.
 The amount of contamination increases the longer the desired precipitate is
left in contact with the mother liquor.
 Immediate filtration should be done if there is possibility of
postprecipitation.
It could be clear from the following example.
Determination of S as HgS: Zn+2 will cause interfere by post precipitation:
ZnS is not readily ppted in the solution with [H+] of about 0.1-0.2, Its
supersaturated solution is highly stable.
But while precipitating HgS, S2- ions are strongly adsorbed on the primary layer,
where solubility product is exceeded, and ZnS will be precipitated. About 90% of Zn
will come down as ppt in 20 min.

In determining Ca- oxalate ; Mg- oxalate will interfere. In absence of CaC2O4, Mg-
oxalate is stable.
Post precipitation can be avoided:
• Using high acidity as possible.
• Filtering the precipitate as fast as possible after the precipitation is complete.
 DRYING AND IGNITION OF PRECIPITATES
After filtration, a gravimetric precipitate is heated until its mass becomes constant.
• Heating removes the solvent and any volatile species carried down with the precipitate.
• Some precipitates are also ignited to decompose the solid and form a compound of
known composition. This new compound is often called the weighing form.
• The temperature required to produce a suitable weighing form varies from precipitate to
precipitate.

• Air drying ( Ambient temp)

• Air drying (low temperature)
• Ignition of precipitate
• Errors during ignition (incomplete removal of water and electrolytes, reduction of
ppt by carbon when filter paper is employed, over ignition leading to decompotion of
substance to indefinite composition, reabsorption of water or CO2 by ignited ppt upon
cooling.)
• Determination of optimum drying and ignition temperature
 Depending upon the nature of precipitate and the impurities,
drying can be done by: Precipitation of AgCl, BaSO 4

• Air drying (Room/ ambient temperature): Some

precipitates like MgNH4.6H2O is air dried by washing with
alcohol. It cannot give accurate result, due to incomplete
loss of water.
Precipitation of Al2O3
• Drying at low temperature (100-1300c): Some
precipitates like AgCl, loss water at this range. It is
laboratory feasible at low cost and is more accurate.
• Drying at high temperature (200 up to 10000c):
Gelatinous ppts like Al2O3, if necessity to get constant
weight by decomposition, to remove strongly adsorbed Precipitation of calcium oxalate
and occluded impurities etc requires higer temperature
for drying and obtaining pure ppt of constant weight. Eg
ignition of CaC2O4 to CaO.
• The temperature at which complete pure precipitate
exists is obtained by plotting mass vs temperature curve
(thermogravimetric curve). Fig: Effect of temperature on precipitate mass.

-H 2 O -C O -C O 2
CaC 2O 4.H2O CaC2O 4 CaCO3 CaO
0 0 0
0 850 c < t
Stable zone 100 c 226-398 c 420-600 c
Precations/errors in ignition:
• Incomplete drying, not removing
impurities
• If precipitate is filtered by paper and get
ignited, it may be reduced by carbon of
filter paper. Thermogravimetric curve
• Should be cooled in desiccators before
weighing otherwise it may absorb water for calcium salicylate.
• Over ignition may loss the composition.
 Organic precipitant • Inorganic: ???

 Reagent forming chelate compounds

 Reagents forming saltlike precipitate
 Advantages and Disadvantages of Organic Precipitants

• Selective or specific,
co-ordinating complex
(at least two
functional group, 5-6
membered ring;
chelation)
• Non polar, less soluble
in water and more in
organic solvents, low
density, intense colour,
not wetted by water,
freed moisture alt low
temperature.
 1. 8-ydroxy quinoline (Oxine)
O

2+
+ Mg N Mg N +
N + 2H
OH
O
+
3+
Al

O O
Al
+
N
N + 3H
O

• Complexation and stability is pH dependent, since the

reaction is depronation ie controlling pH selectivity can
be achieved.
 H3C CH3
2. Dimethylglyoxime
C C

H3C C C CH3 O N N O
2+
N N
+ Ni H Ni H
HO OH O N N O
C C
H3C CH3
Beautiful vivid red color
• Specific to Nickel.
• Precipitation occurs in alkaline solution
• Large weight of complex (bulky); low concentration can be handled
• Dried at 1100c

• Sodium tetra phenyl boron (C6H5)4B-Na+ (Sodium tetraphenyl

borate):
• Form salt like ppt.
• Specific for K+ and NH4+ ions, reaction in 1:1 ratio
• Dried at 105 to 1200c
 organic precipitating agents
Advantages
• Insoluble in water (chelate ppt).
• High molecular weight ; for small amount of metal, less weighing
error.
• Selective and some are specifid (by controlling pH and concentration
of masking agent can be made selective)
• PPt are course and bulky, are easily handled.
• Organic chelates can be titrated after separation in some cases
(indirect titratrimetric method for metal).

Disadvantages:
• All chelates cannot be used, may not be in suitable/good weighing
form, uncertainty in drying.
• Contamination by chelating agent itself, difficult to remove, limited
solubility in water.
• Not easily wetted by water and hence tend to float on the surface of
solution and creep up at the side of the vessel.
 Application of Gravimetric Analysis

 Quantization of inorganic and organic compounds

Lactose in milk, salycylates in drugs, nicotine in pesticides,
cholerestol in cereals etc.
 Elemental analysis: Determination of C and H
 In modern analytical chemistry: Accurate sensitive; it still
has great importance in modern analytical chemistry, can be
faster and more accurate
 Specificity of gravimetric methods
 No necessicity of standardization and calibration.
 Quick test:
• Co-precipitation with gelatinous precipitates is pH dependent
• Homogeneous precipitation is helpful to precipitate gelatinous
precipitates like Ferric hydroxide
• Digestion helps to increase the particle size of precipitates
• Volatile electrolyte like nitric acid is used to wash curdy precipitate like
AgCl
• Occluded impurities are not removed by washing.
• Precipitation from homogenous solution improves the quality of
precipitate.
• Peptization must be avoided in qualitative analysis
• Colloidal particles are electrically charged
• Gelatinous precipitates are not digested
Thank You
Question
Define relative supersaturation. 3marks
How would relative supersaturation affect the particle size obtained from precipitation? 3
What is "thermogravimetric analysis"? Explain briefly why thermogravimetric analysis is usually carried out prior to gravimetric analysis. 4
A sample contains a mixture of ammonium carbonate (NH4)2CO3, sodium carbonate Na2CO3, and sodium chloride NaCl.
Thermogravimetric analysis indicates that a 0.0965 g portion of this sample loses 0.0574 g over a temperature range of 50-75 °C and then
loses another 0.0124 g at 800 °C.

What causes the weight loss at 50-75 °C? 2

What species will remain after being heated to 800 °C? 2
What is the composition of the original sample? 6
Given: Atomic masses: H = 1.008; C = 12.011; N = 14.007; Na = 22.99; O = 15.999; Cl = 35.45.
Example: The phosphorus in a sample of phosphate rock weighing 0.5428g is
precipitated as MgNH4PO4.6H2O and ignited to Mg2P2O7. If the ignited
precipitate weighs 0.2234g, calculate:the percentage of P2O5 in the samplethe
weight of the precipitate of MgNH4PO4.6H2O.(FW P2O5 = 141.94, FW Mg2P2O7 =
222.55 , FW MgNH4PO4.6H2O = 254.40 )(Ans. (a)26.25, (b) 0.4927

31 Exercise:Magnetite is an ore with a formula Fe3O4 or FeO.Fe2O 1.1423g

magnetite ore was solubilized in a concentrated HCl. The Fe 2+ and Fe3+
solutions are all converted to Fe3+ using HNO3. Fe3+ was precipitated as
Fe2O3.xH2O with the addition of NH3. After washing, the filtrate was ignited at
a very high temperature producing 0.5394g pure Fe2O3. Calculate the %Fe and
% Fe3O4 in the sample.(33.32%; 46.04%)

32 Exercise:g phosphate detergent was burnt to lose the organic compounds.

It was then added into a hot HCl to convert P (FW ) to H3PO4.6H2O. After
filtration, the precipitate was then converted to Mg2P2O7 (FW FW=222.57 ) by
ignition. The weight of the remaining compound is 0.2161g. Calculate %P in
https://slideplayer.com/slide/7005389/
the sample.