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Gravimetric AnalysisBy: Dr. O. Rajabi (Pharm.D.- Ph.D.)By: Dr. O. Rajabi (Pharm.D.- Ph.D.)
Associate Professor of ChemistryAssociate Professor of ChemistryDepartment of Medicinal Department of Medicinal ChemistryChemistryMashad University of Medical Mashad University of Medical SciencesSciences
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gravi – metricgravi – metric (weighing - (weighing - measure)measure)
►Definition:Definition:a a precipitationprecipitation or or volatilization volatilization method based on the determination method based on the determination of weight of a substance of known of weight of a substance of known composition that is chemically related composition that is chemically related to the to the analyteanalyte
►analyte - chemical element or analyte - chemical element or compound of interestcompound of interest
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►Reaction:Reaction:aA + rR -----> AaA + rR -----> AaaRRr pptr ppt
where:where: a is # of moles of analyte Aa is # of moles of analyte A r is # of moles of reagent Rr is # of moles of reagent R AAaaRRrr is a pure, insoluble precipitate is a pure, insoluble precipitate
which we can dry and weigh or ignite which we can dry and weigh or ignite to convert to something we can weighto convert to something we can weigh
ppt=precipitateppt=precipitate
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►1914 Nobel Prize to 1914 Nobel Prize to T.W.Richards (Harvard T.W.Richards (Harvard University) for the atomic University) for the atomic weights of Ag, Cl, and Nweights of Ag, Cl, and N
►Richards and his group Richards and his group determined atomic weights determined atomic weights of 55 of the 92 known of 55 of the 92 known elements using gravimetryelements using gravimetry
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T.W.Richards:
►““Every substance must be Every substance must be assumed to be impure, every assumed to be impure, every reaction must be assumed to be reaction must be assumed to be incomplete, every method of incomplete, every method of measurement must be assumed to measurement must be assumed to contain some constant error, until contain some constant error, until proof to the contrary can be proof to the contrary can be obtained.”obtained.”
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7 Steps in Gravimetric 7 Steps in Gravimetric AnalysisAnalysis
► Dry and weigh sampleDry and weigh sample► Dissolve sample Dissolve sample ► Add Add precipitating reagentprecipitating reagent in excess in excess► CoagulateCoagulate precipitate usually by heating precipitate usually by heating► Filtration-separate ppt from Filtration-separate ppt from mother mother
liquorliquor► Wash precipitate (Wash precipitate (peptizationpeptization))► Dry and weigh to Dry and weigh to constant weightconstant weight
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Precipitation:Precipitation:
precipitating agent
sample
dissolvedcomponents
►Dissolve Dissolve samplesample
►Add ppt’ing Add ppt’ing reagentreagent
►FilterFilter►DryDry►WeighWeigh
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Suction FiltrationSuction Filtration
► Filter flaskFilter flask► Buchner funnelBuchner funnel► Filter paperFilter paper►Glass fritGlass frit► Filter adapterFilter adapter►Heavy-walled Heavy-walled
rubber tubingrubber tubing►Water aspiratorWater aspirator
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►Mother liquorMother liquor
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Identify insoluble formIdentify insoluble form
Two considerations:Two considerations: Minimize errors due to limited precipitate Minimize errors due to limited precipitate
solubilitysolubility Minimize errors due to precipitation processMinimize errors due to precipitation process
a.a. Finite solubility of precipitateFinite solubility of precipitate
• ideally, Kideally, Kspsp = 0 (i.e., completely insoluble) = 0 (i.e., completely insoluble)
o Some come close:Some come close: ~10~10-38-38 for Fe(OH) for Fe(OH)33
~10~10-50-50 for Ag for Ag22SS
o For AgCl, KFor AgCl, Kspsp = 1.78 x 10 = 1.78 x 10-10-10
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For example:For example:what would be the what would be the % error% error introduced in gravimetric introduced in gravimetric analysis by the solubility of AgCl?analysis by the solubility of AgCl?
For a 0.1000 g AgCl precipitate in 200 ml HFor a 0.1000 g AgCl precipitate in 200 ml H22O:O:
NoteNote: Error is : Error is independentindependent of of massmass of precipitate, of precipitate, relative error will decrease as precipitate mass relative error will decrease as precipitate mass increases (i.e., 0.038% error for 1.000 g AgCl)increases (i.e., 0.038% error for 1.000 g AgCl)
+ -sp
+ -
K =[Ag ][Cl ]
S =[Ag ] =[Cl ]
-5spS = K =1.33x10 M
-5-4
-4
1.33x10 molAgCl 143.32gAgCl0.200L =3.824x10 gAgCl1L 1molAgCl
3.824x10 gSo, %error : x100 =0.38%0.1000g
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b.b. Precipitation processPrecipitation process
ideally, we’d like a precipitate that ideally, we’d like a precipitate that forms quicklyforms quickly. . This implies:This implies:
Large, pure crystalsLarge, pure crystals Low solubilityLow solubility Easily filteredEasily filtered Easily washedEasily washed
How does precipitation occur?How does precipitation occur?
1.1. As KAs Kspsp is exceeded, solution becomes is exceeded, solution becomes “supersaturated”“supersaturated”
2.2. At some point At some point nucleationnucleation begins begins3.3. At the At the samesame time, time, crystal growthcrystal growth begins begins
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Two points to remember:Two points to remember:1.1. Crystal growth is Crystal growth is independentindependent of degree of supersaturation of degree of supersaturation2.2. Nucleation Nucleation increasesincreases with degree of supersaturation with degree of supersaturation
Minimization Minimization of supersaturation will produce the largest of supersaturation will produce the largest particlesparticles
► Two particle size classesTwo particle size classes
ColloidsColloids ►very smallvery small►difficult to handle experimentallydifficult to handle experimentally
CrystalsCrystals►““large” (~ 10large” (~ 10-1-1 mm) mm)►easily and rapidly filteredeasily and rapidly filtered►high purityhigh purity
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►What affects degree of supersaturation?What affects degree of supersaturation?
KKspsp
Temperature Temperature ►solubility solubility as Tas T
Reagent addition speedReagent addition speed►slower addition givesslower addition gives
precipitation a chanceprecipitation a chanceto begin at lowerto begin at lowersupersaturation levelssupersaturation levels
Solution concentrationSolution concentration►low reagent concentrationlow reagent concentration
equalsequals low supersaturation low supersaturation
ButBut,, even with the above precautions, we will even with the above precautions, we will oftenoften obtain obtain colloidcolloid instead of a crystal! instead of a crystal!
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KeysKeys to successful colloid precipitation: to successful colloid precipitation:1.1. Add precipitant Add precipitant slowlyslowly and in and in slightslight excess excess
2.2. Digest precipitate (Heat, stir, sit)Digest precipitate (Heat, stir, sit)
What about crystalline precipitate?What about crystalline precipitate?Similar to colloids:Similar to colloids:1.1. Dilute solutionDilute solution
2.2. Slow precipitant additionSlow precipitant addition
3.3. Elevated temperatureElevated temperature
4.4. HeatHeat unstirred unstirred Contaminants can escape from crystal latticeContaminants can escape from crystal lattice
Increase crystal bridgesIncrease crystal bridges
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►Particle Size / FilterabilityParticle Size / Filterability produce particles large enough to be produce particles large enough to be
'caught‘'caught‘ ideally, produce crystalsideally, produce crystals avoid colloidal suspensionavoid colloidal suspension
particle size = 1 - 100 nmparticle size = 1 - 100 nm
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Precipitate FormationPrecipitate Formation► crystallizationcrystallization
nucleation:nucleation:particles join to produce aggregatesparticles join to produce aggregates
crystal growthcrystal growthaggregate grows and 'fall out' of solutionaggregate grows and 'fall out' of solution
We want a few big chunks of precipitate!We want a few big chunks of precipitate!supersaturation:supersaturation:
more solute than should be present in more solute than should be present in solutionsolutionrelative supersaturation:relative supersaturation:
a measure of supersaturation, (Q-S)/Sa measure of supersaturation, (Q-S)/SQ = actual solute concentrationQ = actual solute concentrationS = equilibrium solute concentrationS = equilibrium solute concentration
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Controlling PrecipitationControlling Precipitation
►Increase SIncrease S Increase temperatureIncrease temperature
►Decrease QDecrease Q Dilute solutionDilute solution Well mixed (stirring)Well mixed (stirring)
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What Do We Get Out of What Do We Get Out of Gravimetry?Gravimetry?
►% of analyte, % A% of analyte, % A
►%A = %A = weight of analyte weight of analyte x x 100100 weight of sample weight of sample
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How Do We Get %A?How Do We Get %A?
► % A = % A = weight of ppt x gravimetric factor (G.F.)weight of ppt x gravimetric factor (G.F.) x 100 x 100 weight of sampleweight of sample
► G.F. = G.F. = a FW[analyte]a FW[analyte] b FW[precipitate] b FW[precipitate]
►G.F. = # gms of analyte per 1 gm G.F. = # gms of analyte per 1 gm pptppt
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Gravimetric FactorGravimetric Factor
►X apples + Y sugar = Z apple piesX apples + Y sugar = Z apple pies
►What is this relationship in What is this relationship in chemistry?chemistry?
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The Gravimetric FactorThe Gravimetric Factor
►G.F. = G.F. = a FW[analyte]a FW[analyte] b FW[precipitate] b FW[precipitate]
►AnalyteAnalyte pptppt G.F.G.F.CaOCaO CaCOCaCO33
FeSFeS BaSOBaSO44
UOUO22(NO(NO33))22..6H6H22OO UU33OO88
CrCr22OO33 AgAg22CrOCrO44
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►AnalyteAnalyte pptppt G.F.G.F.CaCaOO CaCaCOCO33 CaO/CaCOCaO/CaCO33
FeFeSS BaBaSSOO44 FeS/BaSOFeS/BaSO44
UUOO22(NO(NO33))22 UU33OO88 33UOUO22(NO(NO33))22//UU33OO88
CrCr22OO33 AgAg22CrCrOO44 CrCr22OO33//22AgAg22CrOCrO44
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ProblemProblem
►Consider a 1.0000 g sample Consider a 1.0000 g sample containing 75% potassium sulfate containing 75% potassium sulfate (FW 174.25) and 25% MSO(FW 174.25) and 25% MSO44. The . The sample is dissolved and the sulfate is sample is dissolved and the sulfate is precipated as BaSOprecipated as BaSO44 (FW 233.39). If (FW 233.39). If the BaSOthe BaSO44 ppt weighs 1.4900, what is ppt weighs 1.4900, what is the atomic weight of Mthe atomic weight of M2+2+ in MSO in MSO44? ?
►ANS: MgANS: Mg2+2+
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AnswerAnswer
►The hard part is setting up the The hard part is setting up the correct equation (good correct equation (good stoichiometry skills are essential stoichiometry skills are essential here!):here!):
►Rearranging and solving:Rearranging and solving:
06.96
39.233*25.0
25.174
39.233*75.04900.1
x
)(12.24;06.96
3475.584855.0
2
Mgxx
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ProblemProblem
► A mixture of mercurous chloride (FW A mixture of mercurous chloride (FW 472.09) and mercurous bromide (FW 472.09) and mercurous bromide (FW 560.99) weighs 2.00 g. The mixture is 560.99) weighs 2.00 g. The mixture is quantitatively reduced to mercury metal quantitatively reduced to mercury metal (At wt 200.59) which weighs 1.50 g. (At wt 200.59) which weighs 1.50 g. Calculate the % mercurous chloride and Calculate the % mercurous chloride and mercurous bromide in the original mercurous bromide in the original mixture.mixture.
► ANS: 0.5182 g ANS: 0.5182 g
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AnswerAnswer
►Again, important to set up correct Again, important to set up correct equation:equation:
►Rearranging and solving:Rearranging and solving:
99.560
259.200*2
09.472
*59.200*250.1
xx
gx
x
5182.0
50.127151.08498.0
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Homogeneous PrecipitationHomogeneous Precipitation
(NH(NH22)CO + 3 H)CO + 3 H22O + heat O + heat
HCOOH + OHHCOOH + OH- - + CO+ CO22 + 2 NH + 2 NH44++
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High Electrolyte High Electrolyte ConcentrationConcentration
to Aid Precipitation to Aid PrecipitationExcess charge on colloid creates ionic atmosphere around particle
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Composition by Composition by Gravimetric AnalysisGravimetric Analysis
NiNi2+2+ (aq) + H (aq) + H22DMG DMG Ni(DMG) Ni(DMG)22 + 2 H + 2 H++
►A 0.8234 g org sample produced A 0.8234 g org sample produced 0.1397 g of bis(dimethylglyoximate) 0.1397 g of bis(dimethylglyoximate) nickel (II) (FW = 288.91 g/mol). Find nickel (II) (FW = 288.91 g/mol). Find the nickel content.the nickel content.
►Explain how to create a large, Explain how to create a large, filterable precipitate.filterable precipitate.
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Combustion AnalysisCombustion Analysis
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
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Gravimetric OverviewGravimetric Overview► SimpleSimple►CheapCheap
GlasswareGlassware ReagentsReagents ovens, etc.ovens, etc. BalancesBalances
► SpecificSpecific► Timely Timely (1/2 day)(1/2 day)
► AccurateAccurate► Precise Precise (0.1-0.3 %)(0.1-0.3 %)
► SensitiveSensitive
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