http://www.chem.usu.edu/~sbialkow/Classes/3600/overheads/ Gravimetry/gravimetric.

html Gravimetric A alysis

General Principles In gravimetric analysis measures the mass of a material formed in the reaction of the analyte with the reagent. A chemical reaction for gravimetric analysis is where a moles of analyte A contained in the sample reacts with r moles of the reagent R to form the precipitate AaRr, noted as solid phase (s) in the reaction. Since one does not know the concentration of the analyte before hand, an excess of reagent is used. In electrogravimtery, the reagent is the electron, which is added to the solution bay passage of electrical current at a potential appropriate for oxidation or reduction of the analyte. here are several factors to keep in mind when designing the chemistry! ". here must be a phase change so that the product can be separated from the reaction solution. his is satisfied when the product is a solid precipitated from solution. #. he reaction must be significantly complete. his is satisfied when the Ksp of the product is small. It also means that there are no competing e$uilibria that might re%dissolve the product. &. he final product must be pure and must be of a definite chemical composition. '. he rate of reaction must be fast enough to be practical. he reaction is generally carried out in a flask containing (li$uid%phase) dissolved sample. he reagent solution is added to the reaction flask until the reaction apparently stops. his is detected by noting that there is no longer any precipitate formed upon adding reagent. Separation (hen the reaction is complete, we are left with precipitate containing all, or most of the analyte that was initially in our solution. his precipitate product is subse$uently from the reaction solution using filtration. his is done using one of the several techni$ues discussed in class. )epetitive rinsing of the reaction flask with an electrolyte solution insures $uantitative transfer of the precipitate to the filter paper or crucible. he filtrate must also be pure. o insure purity, the filtrate is rinsed with an appropriate electrolyte solution. An electrolyte solution is used to avoid breaking up the colloids that may be glued together with counter ions (pepti*ation). he electrolyte ions replace ions from the reagent or that might have been present in the analyte solution. he electrolyte should

be volatile and the ions of the electrolyte should not be part of the product complex. +or example, use of ammonium nitrate (,-',.&) or ammonium hydroxide (,-'.-) in distilled water results in the volatile species/ ,-&, -,.&, and -#.. Digestion he precipitate often contains ions that where trapped when the precipitate was formed. his is mostly a problem for crystalline precipitates. If the trapped ions are not volatile, then their presence will corrupt the weighing step. 0oncentration of interfering species may be reduced by digestion. 1igestion is a process where the precipitate is re%dissolved and precipitated out of a cleaner environment (solution). he precipitate obtained in the separation step is placed into a volatile electrolyte solution and heated. 2arge particles are broken up to speed up digestion. his 3solution3 is often heated to increase the kinetic rates of dissolution and precipitation. Since the solid is in dynamic e$uilibrium with the solution, in time, all material will cycle from solid to solution and back. .bservation does not speed up the chemical kinetics, so we take a cola break during digestion. he solution is cooled after digesting for an hour or more. he precipitate is now refiltered. Preparation for Weighing After separation, the material must be prepared for weighing. his is accomplished by heating up the precipitate to drive off excess solvent and volatile electrolytes. 2ow temperature drying may be used for some lyophobic (solvent phobic) precipitates. -igh temperature drying, called ignition, is used for the lyophilic (solvent liking) precipitates. he thing to remember is that drying or ignition may change the chemical composition of the precipitate. Weighing he dried or ignited is solid cooled prior to weighing. his avoids convection currents from altering the mass measurement. he hot sample is placed into a desiccator during the cooling stage to reduce adsorption of water from the air. Since weighing is performed in a vessel, e.g, a weighing bottle or a crucible, the dry weight of the vessel must be determined before hand. he solid weight is determined by difference. More Rules for a Successful Gravimetric Analysis A few additional rules of thumb for a successful $uantitative precipitation are! he precipitate must be large enough to settle out of solution he precipitate must be large enough to be filtered

he precipitation process must be complete he precipitate must be pure he precipitate must be stable when dry, or produce a stable product upon ignition

Example of a Gravimetric Analysis A 4.567# g sample of iron ore is dissolved in perchloric acid (-0l.'). All iron present is oxidi*ed to +e&8. he solution is filtered to remove solid matrix materials and made basic with addition of ammonium hydroxide. he iron precipitates as the +e(.-)& .x-#. gel. he precipitate is collected in a cistern crucible and ignited to produce +e#.&. (hat is the wt. 9 of iron in the sample if the analysis produced 4.&#"4 g +e#.&: irst! examine the chemistry he overall reaction is +rom this we derive the gravimetric factor relating weight of final material to the weight of iron analyte

Secon"! calculate the mass of iron he mass of iron in the ignited precipitate is

#ast! calculate $eight % he weight 9 of iron in the ore is obtained from the mass of iron and the sample weight,

;ack to 0hemistry &744 -ome his page was created by <rofessor Stephen ;ialkowski, =tah State =niversity. 2ast =pdated uesday, August 4&, #44'