gravimetric =measuringmass

y Silicagelgoesfromblueto

pinkasitabsorbsmoisture
Canberegeneratedinoven

y Anhydroussodiumsulfate

getsclumpyasitabsorbs
water

More Information about desiccants including common interferents

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

Coverage
y Typesofgravimetry
y Stepsingravimetricanalysis
y Precipitationgravimetry
y Propertiesofprecipitatesandprecipitants
y Solubilityconsideration&Impurityof

precipitates
y Mechanismofprecipitateformation
y Calculationswithgravimetry&applications
3

GravimetricMethodofAnalysis
` Quantitativemethodsthatarebasedondeterminingthe

mass ofapureelementorcompoundtowhichtheanalyteis
chemicallyrelated.
` Basedonmassmeasurementsmadewithananalytical
balancethatproduceshighlyaccurateandprecisedata.
` Anymethodinwhichthesignalismassorchangein
mass.
` Thereareseveraltypesofgravimetricanalysis;
precipitation gravimetry,volatilization gravimetry,and
electrogravimetry.Theothertwomethodsaregravimetric
titrimetryandatomicmassspectrometry.
4

TypesofGravimetry
` Precipitationgravimetry:methodinwhichthesignalis

themassofprecipitate.E.g..Directdeterminationof
Cl byprecipitationasAgCl
` Electrogravimetry:methodinwhichthesignalisthe
massofanelectrodepositonthecathodeoranodein
anelectrochemicalcell.E.g..OxidationofPb2+andits
depositionasPbO2 ontheanode.ReductionofCu2+ as
Cudepositsonthecathode.
` Volatilizationgravimetry:methodinwhichthelossofa
volatilespeciesgivesrisetothesignal(mass).Thermal
orchemicalenergyisusedtoremovesuchvolatile
compounds.E.gDetermineCinorganiccmpdbyCO2
usingchemicalenergyandmeasuringmassdifference.
5

PrecipitationGravimetry

Cl- + Ag+ AgCl ppt

Mass AgCl precipitate is directly related to
%Cl- in the water sample

7GeneralStepsinGravimetry
y Dry and weigh sample
y Dissolve sample
y Add precipitating reagent in excess
y Coagulate precipitate usually by heating
y Filtration-separate ppt from mother liquor
y Wash precipitate (peptization)
y Dry and weigh to constant weight

PrecipitationGravimetry
` Theanalyteisconvertedtoastableandpure precipitate ofknown

composition.
` Forexample:Cadeterminationmethodinnaturalwatersby
AssociationofOfficialAnalyticalChemist.

+
2+
2Ca + C2O4
NH3

H2C 2O 4

CaC2O4 (s)

2NH4

2-

C2O 4

Ca2+

CaC2O4 (s)
CaO(s)

+ CO(g)+

CO2(g)

` Ca2+ innaturalwatersampledirectlyrelatedtoCaO

CaO

1.PropertiesofPrecipitates
y Lowsolubility

Nosignificantlossoftheanalyteoccursduring
filtrationandwashing
y Highpurity
y Stableunderatmosphericconditions
y Knowncomposition
y Afterdryingandignition,knownchemical
composition
y Easytoseparatefromreactionmixtureandfilteredand
washedfreeofimpurities

2.PrecipitatingReagents:precipitants
y Gravimetricprecipitatingagentshouldreactspecifically

oratleastselectivelywiththeanalyte.

y Specificreagentsreactonlywithasinglechemical

species.E.g..Dimethylglyoxime,isaspecificreagent
thatonlyprecipitatesNi2+ ionsfromalkalinesolutions.

y Selectivereagentsaremorecommonandreactswitha

limitednumberofspecies.E.g..AgNO3,thecommon
ionsthatitprecipitatesfromacidicsolutionsareCl,Br
,I andSCN.

10

Table1.0SelectedGravimetricMethodforInorganicCationsBased
onPrecipitation

11

Table1.0SelectedGravimetricMethodforInorganicAnionsBased
onPrecipitation

12

Organic precipitating agents are chelating agents.

They form insoluble metal chelates.

Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

3.Solubilityconsiderations
y Factorsresponsibleforsolubilitylossofprecipitates

a.. Compositionofsolutioninwhichpptforms
b.. pHofsolution
c.. Solventtype(aqueousandnonaqueous)

14

a.CompositionofSolution
Addonlyenoughprecipitatingreagenttilltheprecipitationisin

dynamicequilibrium,anyextraadditionofprecipitantswillincrease
solubilityofppts.
Ag+ canbedeterminedgravimetricallybyaddingCl asaprecipitant
formingAgClprecipitate.
Considertheequilibrium:
Ag+(aq)+ Cl (aq) AgCl(s)
y OnemightconcludethatadditionofCl atequilibriumwould
increaseprecipitation
however,ithasbeen
observedthatanincreasein
theequilibriumconcentrationofCl
forms
moresolublechloridesandincreases
solubilityoftheAgClppt(fig..)

15

b.pH
2..pHofsolutioninwhichthepptforms.Forexample
hydroxidespptsasFe(OH)3 aremoresolubleatlow
pHswere[OH]issmall.
` Why?AtlowerpHs[H+]isgreaterthereforemore
electrostaticattractionofH+ topptOH occurs,
breakingthepptOHbondandsolvationoccurs.Like
wisepptscontainingacidicionsaremoresolubleat
higherpHswere[H+]islow.Explain.
` Whatissolvation?
` Electrostaticattractionof+and chargedendstothe
pptionsanddissolvingtheppt.

16

c.Solvent Type
..solubilitycanbeaffectedbysolventtype(aqueousor
nonaqueoussolvents)
` Aqueous asolutionwithwaterasthesolvent,ppt
solubilityisgreaterinthissolutionbecausethewater
moleculesstabilizetheionsbysolvation process.
` Nonaqueous solutionwithnowatermainlyorganic
solvents.Organicsolventshavepoorersolvatingability
leadstosmallersolubilityproduct.
` Listsomeexamplesofaqueousandnonaqueous
solventsandexplainhowsolventtypeeffectssolubility
ofprecipitates.

17

4.MechanismofPrecipitateFormation
` Precipitates form by nucleation and by particle growth. If nucleation

`
`

predominates, a large number of very fine particles results; if particle

growth predominates, a smaller number of larger particles is obtained.
In nucleation, a few ions, atoms, or molecules come together to
form stable solid. Often these nuclei form on the surface of suspended
solid contaminants, such as dust particles.
Further precipitation then involves a competition between additional
nucleation and growth on existing nuclei.
If nucleation predominates, a precipitate containing a large number of
small particles results; if growth predominates, a smaller number of
larger particles is produced.
The rate of nucleation is believed to increase vastly with increasing
relative super saturation. On the contrary, the rate of particle growth is
only moderately enhanced by high relative super saturations.
18

ColloidalAgClparticleinasolutioncontainingexcesssilvernitrate.
Positively charged primary
adsorption layer on colloidal
particle
NO3

NO3-

NO3-

H+

Ag
NO3-

Ag

NO3-

Ag

NO3

Cl Ag Cl- Ag+ Cl- Ag+

Ag+ Electric double layer

NO3-

Colloidal Solid
Ag+ Cl- Ag+ Cl- Ag + Cl- Ag+
NO3Ag+
NO3
NO3-

Homogeneous solution
(charged balanced)

Cl- Ag+ Cl- Ag+ Cl- Ag+

Ag+ Cl

Ag + Cl

Ag+

H+
NO3-

Ag +

Ag+ Cl-

NO3

NO3-

Ag +

NO3-

NO3-

Counter-ion layer of
solution with excess anions
NO3-

H+

Ag +

Primary adsorption layer contains adsorbed silver ions. A counter-ion

layer surrounds primary adsorption layer with sufficient excess
negative ions (nitrate, NO3- ions) to balance the charge on the surface
of the particle.

19

5.ExperimentalControlofParticleSize
a,.Supersaturation
` ProblemsfacedduringPrecipitationProcess
Duringtheprecipitationprocess,supersaturation occurs
(thisshouldbeminimized)followedbynucleationand
precipitation.
Supersaturated solutionisanunstablesolutionthatcontains
ahighsoluteconcentration.Withtimesupersaturationis
relievedbyprecipitationoftheexcesssolute.

` Experimental variables that minimize supersaturation

and thus produce crystalline precipitates include

Precipitatefromhotsolutions(increaseTemperature)
Precipitatefromdilutesolutions
Slowadditionofprecipitatingagentwithgoodstirring
ControllingpH

20

b.ColloidalPrecipitates
y Colloidsaresosmalltoholdonafilterandtheycan

settledowninsolutionaswellduetoBrwonianmotion
(stochasticprocess,randomfluctuation).Inorderto
havethecolloidsfilterable,wecancoagulateor
agglomerate.
y CoagulationofColloids:Itcanbehastenedby

heating,stirringandaddinganelectrolyte.

21

6.Impurityofprecipitates:Coprecipitation
` Precipitation

gravimetry is based on known

stoichiometry between the analyte mass and ppt mass ,
therefore precipitate must be free of impurities.
` Greatest source of impurities results from chemical or
physical interactions occurring at the ppt surface.
` A ppt is generally crystalline with a well defined lattice

structure of cations and anions.

` Those cations or anions at the surface carry respectively
a (+) or () ve charge as a result of incomplete
coordination. Example AgCl
` Any impurity in the ppt must be removed before taking
its weight.
22

Coprecipitation:InclusionandOcclusion
y A phenomenon in which otherwise soluble compounds are

removed from solution during precipitate formation.

y There are four types of coprecipitation: Inclusion, surface
adsorption and occlusion.
y Inclusion: chemical species similar to precipitating ions may

substitute into the chemical lattice via chemical adsorption. This

is very difficult to remove but recrystallization process often
minimizes.
y Surface adsorption: soluble compound is carried out of solution on
the surface of coagulated colloid particle. Such easily bound water
can be removed via digestion in mother liquor.
y Occlusion: a compound is trapped within a pocket formed during
rapid crystal growth.

23

7.DryingandIgnitionofPrecipitates
y Afterfiltration,agravimetricprecipitateisheateduntilits

massbecomesconstant.
y Ignitiondecomposesthesolidandformacompoundof
knowncomposition.

24

8.ApplicationsofGravimetricMethods

y 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.
y A variety of organic substances can also be easily
determined gravimetrically. Examples: lactose in milk
products, salicylates in drug formulations, nicotine in
pesticides etc.

25

` Inorganic Precipitating Agents: Table 122 in the

`
`

`
`

textbook.
Reducing Agents: Table 123 shows the reagents can
convert the an analyte to its elemental form.
Organic Precipitating Agents: There are numerous
examples of this type. In one form of organic reagents,
they produce sparingly soluble nonionic coordination
compounds; In the other forms products with largely
ionic bonds.
Organic Functional Group Analysis: See Table 124
in the textbook
Volatilization Gravimetry: Based on volatilization
such as water and carbon dioxide determination.
26

Organicprecipitants
Dimethylglyoxime

8-Hydroxquinoline (oxine)
+

2
N
OH

2+

Mg

Mg

2H

O
27

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
28

How Do We Get %A?

% A = weight of ppt x gravimetric factor (G.F.) x 100
weight of sample

G.F. =

Molar mass of analyte

Molar mass of precipitate

X a (mol analyte/mol ppt)

b

a: mole analyte; b. mole precipitate

Hence, a/b give mole ration fraction

G.F. = # grams of analyte per 1 gram

precipitate
29

The Gravimetric Factor

G.F. =

Mr. analyte X a (mol analyte/mol ppt)

Mr. precipitate b

Analyte
CaO
FeS
PbCl2
UO2(NO3)2.6H2O
Cr2O3

ppt
G.F.?
CaCO3
BaSO4
PbCrO4
U 3O 8
Ag2CrO4
30

Gravimetric Factor
Analyte

ppt

G.F.

CaO
FeS
PbCl2

CaCO3
BaSO4
PbCrO4

CaO/CaCO3 x 1/1
FeS/BaSO4 x 1/1
PbCl2/PbCrO4 x 1/1

UO2(NO3)2
Cr2O3

U3 O8
Ag2CrO4

3UO2(NO3)2/U3O8 x 3/1
Cr2O3/2Ag2CrO4 x 1/2

31

Example 10.1:

Ref: Gary D Christian 6th ed p-323

An ore is analyzed for the manganese

content by converting the manganese to
Mn3O4 and weighing it. If 1.52-g sample
yields Mn3O4 weighing 0.126-g, what
would be the percent Mn2O3 in the
sample? The percent Mn?
Molar mass:
Mn2O3=157.9; Mn3O4= 228.8; Mn=54.94
32

Example 10.2:

Ref: Gary D Christian 6th ed p-323

Orthophosphate (PO33-) is determined by

weighing as ammonium phosphomolybdate,
(NH4)PO4.12MoO3. Calculate the
percentage P and P2O5 if 1.1682-g
precipitate ere obtained from a 0.2711-g
sample.
Molar mass:
(NH4)PO4.12MoO3 =1876.5; P2O5= 141.95;
P=30.97
33

Example 10.3:
The Aluminum in a 0.910g sample of impure
ammonium aluminum sulfate was precipitated
with aqueous ammonia as the hydrous
Al2O3.xH2O. The precipitate was filtered and
ignited at 1000oC to give anhydrous Al2O3,
which weighed 0.2001g.
Express the result of this analysis in terms of:
a. % Al2O3

b. % Al in the sample.
34

Example 10.4
y

An iron ore was analyzed by dissolving a

1.1324-g sample in concentrated HCl. The
resulting solution was diluted with water
and iron (III) was precipitated as the
hydrous oxide Fe2O3.xH2O by the addition
of NH3. After filtration and washing the
precipitate was ignited to give 0.5394-g of
pure Fe2O3 (159.69 g/mol).
Calculate the % Fe (55.847 g/mol), %
Fe3O4 (231.54 g/mol) in the sample.
35

y Example: 10.5
Thecalciumina200.0mL sampleofanaturalwater
wasdeterminedbyprecipitatingthecation as
CaC2O4.Theprecipitatewasfiltered,washed,and
ignitedinacruciblewithanemptymassof26.6002
g.ThemassofthecrucibleplusCaO (fwt 56.077
g/mol)was26.7134g.Calculatetheconcentration
ofCa(fwt 40.078g/mol)inthewaterinunitsof
gramsper100mL.

y Example 10.6
y Anironorewasanalyzedbydissolvinga1.1324g
sampleinconcentratedHCl.Theresulting
solutionwasdilutedwithwater,andtheiron(III)
wasprecipitatedasthehydrousoxideFe2O3.xH2O
byadditionofNH3.Afterfiltrationandwashing,
theresiduewasignitedathightemperaturetogive
0.5394gpureFe2O3 (fwt 159.69g/mol).Calculate
(a)the%Fe(fwt 55.847g/mol)and(b)%Fe3O4
(fwt 231.54g/mol)inthesample.

y Example 10.7
y A0.2356gsamplecontainingonlyNaCl (fwt 58.44
g/mol)andBaCl2 (fwt 208.23g/mol)yielded0.4637
gofdriedAgCl (fwt 143.32g/mol).Calculatethe
percentofeachhalogencompoundinthesample.

MoreReviewQuestions
1.Differentiatebetweenthefollowing;
Precipitationgravimetry,volatilizationgravimetry &electrogravimetry
Digestionandpeptisation
Inclussion &Occlusion
Selective&specificprecipitatingreagents(giveexamples)
2.DescribeusingAgCl,themechanismsofprecipitateformation?
3.Describethethreemostimportanttypesofcoprecipitation thatmayoccur
duringprecipitateformationandstatewaysinwhichsuchimpuritybe
minimizedorremoved?
4.Explainthefollowingfactorsresponsibleforsolubilitylossofprecipitate?
a. Compositionofsolutioninwhichppt forms
b. pHofsolution
c.Solventtype(aqueousandnonaqueous)

G5502 Analytical Chemistry 2011(C)

39

MoreReviewQuestions
1.Treatmentofa0.2500gsampleofimpurepotassiumchloridewithanexcessofAgNO3

resultedintheformationof0.2912gofAgCl.CalculatethepercentageofKCl inthe
sample.(MolarmassAgCl 143.321g/mol,KCl 74.551g/mol)
2.Anironorewasanalyzedbydissolvinga1.1324gsampleinconcentratedHCl.The
resultingsolutionwasdilutedwithwaterandiron(III)wasprecipitatedasthehydrous
oxideFe2O3.xH2ObytheadditionofNH3.Afterfiltrationandwashingtheprecipitate
wasignitedtogive0.5394gofpureFe2O3 (159.69g/mol).
3.Calculatethe%Fe(55.847g/mol),%Fe3O4 (231.54g/mol)inthesample.
Thealuminumcontentofanalloyisdeterminedgravimetricallybyprecipitatingitto
Al(C9H6ON)3.Ifa1.021gsampleyielded0.1862gofprecipitate,whatisthepercent
aluminuminthealloy?
4.Statetheproblemoftenfacedduringprecipitationprocess.Howcanyouaschemists
minimizeit?
5.Whatarethestepsinvolvedingravimetricanalysis?

G5502 Analytical Chemistry 2011(C)

40