CAPE Analytical Methods and Separation Techniques = Gravimetry GRAVIMETRIC METHODS OF ANALYSIS Gravimetric analysis refers to any method of chemical analysis that involves accurate weighing in the final step of the analysis. It involves the conversion of an element, ion or radical to a pure stable substance suitable for weighing. Accurate mass measurements are made with an analytical balance. Gravimetric analysis describes a set of methods in analytical chemistry for the quantitative determination of an analyte based on the mass of a solid. Advantages: 1. Accurate and precise when using modern analytical balances, 2. Possible sources of error are readily checked, since filtrates can be tested for completeness of precipitation and precipitates can be examined for the presence of impurities 3. It is an absolute method — involving direct measurement 4, Relatively inexpensive apparatus:- most expensive requirements are analytical balance , the mufile furnace and in some cases platinum crucible NB: Sometimes the element being analysed is in one form, but must first be converted to a different form before quantitative analysis can take place. Usually an acid would be used to convert the analyte which is a solid to an aqueous solution which can then be precipitated by an known amount of precipitating reagent. Hither HCl or HNOs is used, if the substance is a carbonate, the acid can be dilute, otherwise the concentrated version of the acid is used. ‘Types of gravimetry: + Precipitation + Volatilization Precipitation ‘This form of analysis entails converting the substance being analysed (analyte) into a sparingly soluble precipitate of known composition that can be weighed. The conversion is assisted by the use of a precipitating agent. Precipitating agent Precipitate ‘Silver nitrate, AgNOs Silver halides: AgCl, AgBr, Agi ‘Barium chloride, BaChy BaSOy Hydréchloric acid, HCL ‘AgCl ‘Sulphuric acid, HySOg PDSO«, BaSOy ‘Aqueous ammonia, NH ‘AlAOs, Fer0s Page 1 of 8 ‘Scanned with CamScannerCAPE Analytical Methods and Separation Techniques Gravimetry Procedure: 1, The substance being analysed is weighed in a stoppered bottle 2. The substance is then placed in a beaker and made into a solution using distilled water 3. Anexcess amount of the precipitating agent is then added (which reacts with the substance being analysed) and the mixture stirred 4, The mixture is then filtered usually by vacuum filtration 5. The residue is washed with distilled water to remove impurities. Care must be taken when ‘washing the precipitate to prevent redissolving, (wash no longer than is necessary, use small amounts of water and washing with a solution containing an ion which is common to the one in the precipitate makes it less likely that any precipitate will redissolve) 6. The residue is dried and heated in an oven and then cooled in a dessiccator (containing silica ¢geV/soda lime/ phosphorus(V) oxide) until a constant mass is obtained 7. Knowledge of the mass and chemical composition of the precipitate formed, can be used to calculate the mass of a particular chemical component (anion or cation) of the original sample. 8, Finally, from the mass of the component and the mass of the original sample, we can determine the percent composition by mass of the component in the original compound. a Sintered > 2 glass filter jintered-glass soe fiter ae | Precipitate crucible me —> to suction ~~~ _ pump Vacuum pump b US porcelain Peper base with holes . Filtrate Figure 8.6.1 Two pieces of apparatus for filtrtion; aA sitered-glass crucible: bA suction funnel (Buchner funnel) — Filtration is done using a suction flask and Buchner funnel. — All solids must be transferred to the funnel by thoroughly washing the container containing the precipitate — ‘The pump is tumed on and the liquid to be filtered is directed into the sintered-slass crucible Page 2 of 8 ‘Scanned with CamScannerCAPE Analytical Methods and Separation Techniques Gravimetry Characteristics of precipitate: An ideal precipitating agent must react with the analyte to give a precipitate that is: — Large crystals — Easy to filter — Can be easily washed free of impurities — Must have a very low solubility to minimise the loss of precipitate in filtration and in the washing process — It must be unreactve with the substances in air — Itmust be stable and of fixed composition. The composition must not change during the drying process — Have a high purity. It is difficult to obtain a product which is pure, but careful precipitation and sufficient washing helps reduce the level of impurity ‘Unwanted precipitation may occur with the desired product called coprecipitation. It cannot be avoided but can be reduced by slow precipitation and thorough washing. The precipitate should consist of crystals large enough to be easily washed and filtered. Large crystals also have smaller surface areas for surface absorption of foreign material. Caleut The treatment of a 0.800g sample of impure KCI with excess aqueous AgNOs resulted in precipitation of 1.460g of AgCl. Calculate the % KCI in the sample, # of moles in 1.460g of AgCl = 1.460/ 143.5 = 01 mole ‘Since 1 mole AgCl is formed from 1 mole of CI ions As‘ + Clay —* AgChy And 1 mole of CI ions is formed from 1 mole KCI ka => K’ + cr The # of moles of KCI reacted = 0.01 mole ‘The mass of 0.01 mole of KCI=0.01 x 74.5 = 0.745g Thus the % KC] in the sample = 0.745/0.800 x 100= 93.13% ACTIVITY 1. 2g ofa silver salt was dissolved in water, An excess amount of HCI was added. The ppt was washed and dried. After the process the mass was found to be 1.89g. Calculate the percentage of silver in the sample. 2. A sample of a lead salt was analysed by using NazCrO, solution. The following results were obtained: Mass of sample + weighing bottle = 12.0824g; Mass of weighing bottle = 10.732g 200 cm’ of 1 molar NazCrO, was added. The ppt formed was filtered, dried and weighed: Mass of crucible and salt = 14.832g; Mass of crucible = 12.813g Seande 10 832-12) hw 100 Mere = | B50y 5 De 2 Page 3 of 8 mel | 2.095 ‘Scanned with CamScannerCAPE Analytical Methods and Separation Techniques Gravimetry Calculate the percentage of lead in the sample, [Pb = 207; Cr= 52; 0= 16] - Volatilization Precipitation In this method of gravimetric analysis, the substance being analysed is converted (by heating) to a stable ‘gas of known composition. The gas can be collected and weighed or the mass of product can be determined indirectly from the loss in mass of the sample: The gas produced may come from direct heating of the analyte or by adding a chemical. Example: The determination of the water or CO; content of a sample is usually done by volatilization. Direct determination: Of water, water vapour is collected on a solid desiccant and its mass determined from mass gained by the desiccant. The mass of CO; evolved by the decomposition of carbonates is determined by the increase in weight of a solid dessicant. Indirect determination: The sample is heated and mass of water lost from sample is determined from loss in mass of sample. Examples: MgSO,.7H:0) —» MgSO + TEhOwp NaHCOm) + HCky + NaChg + HO + COxp Example: The sodium bicarbonate content of antacids is determined by the volatilization of CO2 NaHCOx + HaSOmy — CO + ThOg + NaHSOx) The material in a tube retains CO»: a 2NaOH + CO: + NaxCOs(massis measured) + 120 Nagas used to flush tubes and remove 20g & CO) —> atmosphesi: co: ‘NaOH on non fibrous slieate and CaSO4 Renmisture ey NaHCOs + H,SOs Daiesite (C0804) Calculation: A 2.5g sample of impure CaCO was decomposed with excess HCl. The liberated CO collected in an absorbent was found to weigh 0.88g. calculate the % of CaCOs in the sample. Page 4 of 8 ‘Scanned with CamScanner_ CAPE Analytical Methods and Separation Techniques Gravimetry # of moles in 0.88g of CO2 = 0.88/44 = 0.02 mole CaCO; + 2HCI + CaCl + CO; + H,0 1 mole of CO; is formed from 1 mole CaCOs ‘Therefore, 0.02 mole of CaCOs was used in the reaction Mass of CaCOs used = 0.02 x 100= 2g % CaCOs in sample = 2/2.5 x 100= 80% ACTIVITY: 1. A sample of hydrated CuSO, was heated to determine the number of moles of water of ‘crystallisation. The following results were obtained: Mass of CuSO, + test tube before heating = 16.94 Mass of CuSO, + test tube after heating = 14.843g Determine the number of moles of water of crystallisation in the sample. [Cu= 63.5; 0=16; $=32;H=1] 2. 3g of sample of impure NaHCO was reacted with an excess amount of HCl. The COxe) produced was absorbed by passing through a container with NaOH. The following results were obtained: Initial mass of vessel + NaOH = 24.3188 Final mass of vessel + NaOH = 24,8046 Determine the percentage NaHCOs in the sample. Basic apparatus used in gravimetry Suction funnel (Buchner funnel) Used for filtering large quantities of material. It consists of a crucible made of porcelain with a solid base plate having several holes in a concentric pattem. For filtration the suction funnel requires appropriately sized filter paper to fit over the base to cover the holes. Suction flask (Filter flask or Buchner flask) This is a conical shaped flask of heavy glass with a side arm for applying a vacuum, ‘When ready for filtration, the filter paper in the filter funnel is moistened with solvent and the funnel attached to the filter flask. A vacuum is applied to the filter flask via a filter pump or vacuum pump. The filter funnel collects the filtrate from the filtration of a precipitate, Refer to diagram below, ica crucibles Page 5 of 8 ‘Scanned with CamScannerCAPE ‘Analytical Methods and Separation Techniques Gravimetry Used for heating or igniting small quantities of precipitates, The crucible has a lid to prevent loss of material during heating or ignition. These crucibles are used for quantitative work in which the dry mass of an ignited precipitate or solid must be accurately determined. Sintered glass crucibles It allows for filtering, drying and weighing of a precipitate directly, The crucible is made of resistance glass and has a porous disc of sintered ground glass fused into the body of the crucible. Ovens and Furnaces Ovens are used for drying samples at temperatures ranging from 40 - 300°C. Furnaces are used for igniting samples above 300°C. Desiccators ‘These are used to store recently dried/heated samples to prevent the absorption of moisture and exposure to air. They contain a drying agent or desiccant e.g. anhydrous CaCl, MgO, MgSOx, K2COs, KOH, anhydrous NazSOs (gets clumpy as it absorbs moisture), H2SO., ZnCh, silica gel (tums from blue to pink). Page 6 of 8 ‘Scanned with CamScannerCAPE FIG 23.4. Buchner funnel (porcelain) Buchner Flask Analytical Methods and Separation Techniques Gravimetry Buchner funnel and flask for filtration under reduced pressure Filter paper Small holes in integral platform in the funnel — > To vacuum pump Page 7 of 8 Scanned with CamScannerCAPE Analytical Methods and Separation Techniques Gravimetry Gravimetric analysis in quality control - Gravimetric analysis has been used in the determination of and / or quality control of: + Moisture content in foods e.g. cereals ‘© Essential elements in vegetables such as * Nicotine in pesticides phosphorus * Cholesterol in cereals © Lactose in milk * Chloride ions in water supply (as AgCl « Phenolphthalein in laxatives | ppt) * Salicylates in drugs © SO; in drinks and as a pollutant in air (as ‘© Benzaldehyde in almond extracts BaSOx ppt) ACTIVITY: 1, The calcium content in a 400mL sample of water was determined by precipitation gravimetry as calcium oxalate. After precipitation, filtration, washing, drying and ignition, the dry mass of CaO and crucible was found to be 30.7257g. mass of empty crucible was 30.6123g. Calculate the concentration of calcium in the water sample, expressed in M and wiv%. 2. A compound of Iron (Fe) and Chlorine (Cl) is soluble in water. An excess of Silver Nitrate (AgNOs) was added to precipitate the chloride ion as silver chloride. Ifa 134.8 mg sample of the ‘compound gave 304.8 mg of AgCl, what is the formula of the compound? 3. Hydrated ammonium iron (1) sulphate has the formula (NH,)zSO;.FeSO,.xH2O. 8.73g of the salt was made up to 250 cm’ of solution using water and dilute sulphuric acid. 25.0 cm’ portions of this solution reacted with an average 22.3 cm° of 0.0200 mol dm® potassium manganate (VII_) solution. Find the value of x (water of crystallization), Equation. MnOdjq +-SFe%aq +-8H aq) + Mn*q)-4--SFe™ aq + 4420 Refer to pg 795 AS/A Level chemistry 02 Page 8 of 8 ‘Scanned with CamScanner