GRAVIMETRIC METHODS

What is it?
A gravimetric analysis is based upon the measurement of the weight of a substance that has a KNOWN composition AND is chemically related to the analyte. any method in which the signal is a mass or change in mass direct method: determine the mass of the analyte itself, or the mass of a compound containing the analyte. indirect method: measure a change in mass due to its loss, or the mass of a compound formed as the result of a reaction involving the analyte

Direct method
measure an analytes mass directly by placing it on a balance and recording its mass.

pass it through a preweighed filter that retains the suspended solids. After drying to remove any residual moisture, you weigh the filter. The difference between the filters original mass and final mass gives the mass of suspended solids.

Direct method
Case: Pb2+/ solution cannot isolate the analyte by filtration because the Pb2+ is dissolved in the solutions matrix. measure the analytes mass, however, by chemically converting it to a solid form. suspend a pair of Pt electrodes in the solution and apply a sufficiently positive potential between them for a long enough time Pb2+(aq) + 4 H20(l) PbO2(s) + H2(g) + 2H3O+(aq) Pt anode weigh the Pt anode before and after applying the potential the mass of PbO2 the mass of Pb2+. a direct analysis because the material being weighed contains the analyte.

Determination of the amount of water in a sample

(1) heat the sample to a temperature at which the water in the sample vaporizes. capture the vapor in a preweighed absorbent trap the change in the absorbents mass (2) weigh the sample before and after heating using the change in its mass as an indication of the amount of water originally present.

Direct analysis

Indirect analysis

phosphite, PO33, reduces Hg2+ to Hg22+. In the presence of Cl a solid precipitate of Hg2Cl2 forms.

If HgCl2 is added in excess, each mole of PO33 produces one mole of Hg2Cl2. The precipitates mass, therefore, provides an indirect measurement of the mass of PO33 present in the original sample.

Types of gravimetric methods

1) Precipitation methods: analyte is precipitated by a reagent that yields a sparingly soluble product that has a known composition or can be converted to such a substance (When the signal is the mass of a precipitate). 2) Volatilization methods: analyte or its decomposition products are volatilized The volatile product is collected and weighed or the mass of the product determined from the weight loss in the mass of sample 3) Electrogravimetric methods: analyte is deposited on an electrode 4) Particulate gravimetry: the analyte is determined following its removal from the sample matrix by filtration or extraction.

Applications
One of only a small number of techniques whose measurements require only base SI units, such as mass and moles. Estimating the composition of materials Extensive numbers of inorganic ions are determined with excellent precision and accuracy. Routine assays of metallurgical samples. Relative precision 0.1 to 1%. Good accuracy

Apparatus
Flasks, beakers, pipettes, crucibles, filter papers, vacuum
filter. Centrifuge (device in which solid or liquid particles of different densities are separated by rotating them in a tube in a horizontal circle. The dense particles tend to move along the

length of the tube to a greater radius of rotation, displacing the

lighter particles to the other end) Oven or furnace and a desiccator. Analytical quality balance.

centrifuge

Precipitation Gravimetry
Precipitating agent = precipitant
1) low solubility, of high purity, and of known composition 2) easy to separate from the reaction mixture

Precipitate (an insoluble compound )

any reaction generating a precipitate can potentially serve as a gravimetric method.

To provide accurate results, a precipitates solubility must

be minimal. The accuracy of a total analysis technique typically is better than 0.1%, which means that the precipitate must account for at least 99.9% of the analyte.

1)
2) 3) 4) 5) 6)

7)

Weigh the sample or substance that need to be analyzed Dissolve sample Add precipitating agent Filter Wash Dry (general: heating then, cool it down in a desiccator) Weigh (Repeat the drying and weighing process till you get the constant mass of the precipitate).

An incomplete precipitation or incomplete drying or cooling can cause errors in finding out the actual mass of the analyte.

Properties of precipitates and precipitating agents

The ideal precipitating agent will react specifically or, if not, selectively with the analyte
specifically (rare): reactly only with a single chemical species. dimethylglyoxime Ni2+ selectively (common): react with a limited number of species. AgNO3 Cl-, Br-, I- & SCN-

Precipitate should be easily filtered and washed free of contaminates Precipitate should be essentially insoluble to prevent washing loss Precipitate should be of known composition A stable product; no oxidation, dehydration or gelatinous precipitates. Must avoid side reactions which result in coprecipitates.

Inorganic precipitating agents

Organic precipitating agents are chelating agents. They form insoluble metal chelates.

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

Mechanism of Precipitation
Nucleation - Fast combination of a few atoms, often on the surface of dust particles. Very difficult size to filter and separate. Particle Growth - occurs more slowly, and at lower relative supersaturation of the solution.

Particle size and filterability of precipitates

Colloidal suspensions 10-7 to 10-4 cm diameter ex: Fe(OH)3 (gelatinous) Normally remain suspended Very difficult to filter convert into a filterable solid: coagulation (the reverse process is called peptization)
Crystalline suspensions (ideally) above tenths of mm diameter ex: BaSO4 Normally settle out spontaneously Readily filterable

Particle size and filterability of precipitates

Precipitation reactions are generally slow >< supersaturation is very likely. HIGH supersaturation: a large number of small particles

is formed.
LOW supersaturation: a small number of large particles is formed a crystalline suspension. the goal in precipitation reactions is to minimize supersaturation conditions.

Relative supersaturation (RS)

Q: concentration of the solute at any instant S: equilibrium solubility RS precipitate size (colloidal) RS precipitate size (crystalline solid)

Experimental Control of Particle Size

* RS, Q, S particle size 1. dilute sample solution and dilute reagents (Q) 2. slow addition of precipitating agent with good stirring (Q) 3. in hot solution (S) 4. pH control, acidity solution (S) ex: precipitation of calcium oxalate a. in mildly acidic, calcium oxalate large, easily filtered crystals (moderately soluble) b. adding aqueous ammonia pH completed precipitates *Precipitates with very low solubilities, such as many sulfides and hydrous oxides, generally form a colloids.

Important Factors for Gravimetric Analysis

Coagulation, agglomeration Suspended colloidal particles coalesce to form larger filterable particles (inert electrolyte allows closer approach) Digestion Precipitation heated for hour(s) in contact with solution from which it was formed Peptization Re-dissolution of coagulated colloids by washing and removing inert electrolyte

Co-precipitation
Normally soluble compounds are carried out of solution by a precipitate (surface adsorption, occlusion, mixed crystals, entrapment)

Coagulation (or agglomeration) of colloids: converting a colloid suspension into a filterable solid. Adsorption: a process in which a substance (gas, liquid or solid) is held on the surface of a solid. In contrast, absorption, involves retention of a substance within the pores of a solid. Electric double layer: Primary adsorption layer primary adsorbed ion: 1. lattice ions which in excess. 2. held by chemical bound 3. fixed on precipitate surface ex: AgCl in excess Ag+ AgCl:Ag+(s) Counter-ion layer counterions (secondary adsorption layer) 1. opposite charge of primary adsorbed ion 2. held by electrostatic attraction 3. loosely held in solution surrounding the precipitate ex: AgCl in excess AgNO3 AgCl:Ag+ NO3-(s)

The neutral double layer causes the colloidal particles to coagulate.

solidsolution interface at a particle of AgCl in a solution containing excess AgNO3

a solution of AgNO3 using NaCl as a precipitant

Coagulation of a colloidal suspension

Coagulation cannot occur if the secondary adsorption

layer is too thick because the individual particles of

AgCl are unable to approach one another closely

enough.

Coagulation of a colloidal suspension

1. Decreasing the number of chemically adsorbed Ag+ ions: add additional NaCl precipitating more of the excess Ag+ the number of chemically adsorbed Ag+ decreases coagulation occurs >< Adding too much NaCl, however, creates a primary adsorption layer of excess Cl- with a loss of coagulation. 2. Increasing the concentration of inert ions: add an inert electrolyte increase the concentration of ions in the secondary adsorption layer shrinkage of the secondary absorption layer particle can then approach one another more closely and agglomerate. 3. Heating: a. Decrease number of adsorbed ions in the primary adsorption layer lowering the precipitates surface charge b. Increase the particles kinetic energy allowing them to overcome the electrostatic repulsion that prevents coagulation at lower temperatures.

electrostatic repulsion between the two positively charged particles

Decreasing the charge within the primary adsorption layer

Adding additional inert ions

Digestion
Helps eliminate colloidal suspensions which are difficult or impossible to filter Digestion occurs when a precipitate is allowed to stand in its heated solution (unstirred) The solid re-dissolves and precipitates, along with increased crystal growth The resulting solid is usually more filterable and purer Minimizes coprecipitation
During digestion at elevated temperature: Small particles tend to dissolve and reprecipitate on larger ones. Individual particles agglomerate. Adsorbed impurities tend to go into solution.

Peptization
A process by which a coagulated colloid returns to its dispersed state (a coagulated precipitate reverts to smaller particles) May happen during washing precipitate (Washing with water will dilute the counter layer and the primary layer charge causes peptization) Prevented by washing precipitate with a solution of an electrolyte that can be volatilized on heating. Ex: AgCl, washed with a dilute HNO3 (a NO3- ion stuck to one particle can attract Ag+ ions stuck to other particles: wash with HNO3 a high electrolyte concentration is maintained and the AgCl particles stay clotted together dry the precipitate: the acid decomposes and volatilizes, so it shouldn't have a strong effect on the precipitate mass).

Coprecipitation
Coprecipitation is the process in which soluble compounds are removed from solution during the formation of precipitates.
Surface Adsorption - most pronounced on colloids with large surface areas. Brings along equilibrium surface contamination. Reprecipitate. processes Mixed-Crystal Formation - Replacement of one of the ions in the crystal by another ion. Occlusion - When a crystal is growing rapidly arise during precipitate formation, foreign ions in the from the counter-ion layer may become trapped, or kinetics of occluded, within the growing crystal. Mechanical Entrapment - entrapment of crystal growth foreign substances when two adjacent growing crystals grow together to form one

Surface Adsorption
specific surface areas(SA) adsorption
SA = (cm2)/mass(g)

SA = 1000 0.12 6 = 60 cm2 SA = 11 6 = 6 cm2

A coagulated colloid

Ex: in chloride analysis primary adsorbed ion : Ag+ counter-ion layer : NO3- or other anions AgNO3 (normally soluble) is coprecipitated with the AgCl.

Methods for Minimizing Adsorbed Impurities on Colloids a. Digestion: particle size specific surface area adsorption b. Washing with volatile electrolyte solution Ex: in Ag+ analysis, primary adsorbed ion : ClWashing with an acidic solution counter-ion layer : H+ HCl volatilized when precipitate is dried c. Reprecipitation, double precipitation The filtered solid is redissolved and reprecipitated. The first precipitate ordinarily carries down only a fraction of the contaminant present in the original solvent. the solution containing the redissolved precipitate has a significantly lower contaminant concentration than the original, and even less adsorption occurs during the second precipitation.

Mixed-Crystal Formation
a contaminant ion replaces an ion in the lattice of a crystal the same charge the size differ < 5 % salt : the same crystal class Ex: (a). PbSO4 in BaSO4 BaCl2 + solution containing sulfate, lead & acetate BaSO4 + PbSO4 (Pb + acetate lead acetate) (b). MgKPO4 in MgNH4PO4 (c). SrSO4 in BaSO4 (d). MnS in CdS

Minimizing Coprecipitation
Accomplished by carefully controlling solution conditions Precipitate less soluble interferent precipitates and filter them Mask analyte or interferent with a suitable complexing agent to prevent precipitation

Precipitation from Homogeneous Solution

Homogeneous precipitation is a process in which a precipitate is formed by slow generation of a precipitating reagent homogeneously throughout a solution.
Solid formed by homogeneous precipitation are generally purer and more easily filtered than precipitate generated by direct addition of a reagent to the analyte solution. the level of supersaturation remains low and compact crystal precipitates usually result instead of coagulated colloids.

flocculent, low density

settle in a thin layer on the bottom

Filtration
Usually accomplished with filter paper or fritted glass crucibles Pore size should be chosen carefully to retain analyte particles but not clog

Filter paper must usually be removed by ignition but this

requires a low ash paper Filtering process begins by decanting the supernatant liquid through the filter medium, followed by the solid with wash

Washing
Wash out all impurities but leave it unchanged in composition. Remove the remaining supernatant. Avoid solubility losses Use of cold solvent often accomplishes this goal pH adjustment may be necessary for acids and bases

A volatile inert electrolyte may be added to avoid

peptization
Precaution: Factors cause the precipitate to dissolve back into the solvent !

Drying Precipitates
After the precipitate is filtered, it is heated until its mass becomes constant. The primary purpose of this is to drive off any solvent and any other volatile species that may be present. The temperature and time required to produce a

suitable product varies from precipitate to precipitate.

Some

precipitates

are

also

ignited.

This

process

decomposes the solid, whose exact composition may not be

known, and forms a new compound of known composition. This new compound is called the weighing form.

Gravimetric Calculations
Gravimetric calculations are usually expressed as wt % Careful attention must be paid to the stoichiometry of the process 1) Write the balanced chemical equation for the precipitation reaction. 2) Calculate the moles of the precipitate using this formula: moles = mass/ molecular mass 3) Using the moles ratio of the analyte, calculate the moles of analyte from the balanced chemical equation. 4) Calculate the mass of the analyte using this formula: mass = moles x molecular mass 5) Calculate the percentage using this formula: % analyte in sample = (mass analyte/mass sample)x100.

Gravimetric Calculations
Often it is convenient to use the stoichiometry to calculate a gravimetric factor, g, that can be used to find the desired result

Gravimetric Calculations
If you were looking for SO3 and your precipitate was BaSO4, the gravimetric factor would be:

The numbers, 80.064 and 233.391, are the formula weights (or molecular mass) of SO3 and BaSO4, respectively. How to determine the mole ratio entire reaction? Simply balance the common element. Most of the time oxygen is not considered. In the above example, sulfur appears in both terms. without knowing the There is only one sulfur in each term and the sulfurs are balanced. In other words, the mole ratio is 1.

The common element is silver, Ag. There are two silver atoms represented in the upper term and only one in the lower term. To "balance" the silver atoms, a 2 is placed in front of the substance in the lower term.

The calculation set-up for this gravimetric factor would be:

EXAMPLE
An iron ore was analyzed by dissolving a 1.1324 g sample in concentrated HCl. The resulting solution was diluted with water, and the iron(III) was precipitated as the hydrous oxide Fe2O3 xH2O by the addition of NH3. After filtration and washing, the residue was ignited at a high temperature to give 0.5394 g of pure Fe2O3 (159.69 g/mol). Calculate (a) the % Fe (55.847 g/mol) and (b) the % Fe3O4 (231.54 g/mol) in the sample.

Solution 1
Amount of Fe2O3 (mol) (a) Amount of Fe (mol) Mass of Fe (g) % Fe (b) Amount of Fe3O4 (mol) Mass of Fe3O4 (g) % Fe3O4

Solution 2

1) Calculate gravimetric factors

2) Calculate the %

Critique
Time require less operator time and no calibration.

The results are calculated directly from the experimental

data and requires only the gravimetric factor and molar masses Equipment Simple, reliable, relatively inexpensive and easy to maintain.

Sensitivity and Accuracy limited by the devices used for measurements. the analytical balance is the limiting measurement

device (Scrupulously clean glassware, very accurate

weighing). other factors: solubility losses, coprecipitation errors, and mechanical losses of the precipitate. Gravimetric methods are the method of choice, particularly

if the analyte concentration in the sample is larger than 1%.

Other analytical methods should be considered for analyte concentrations less than 0.1%.

Specificity Reagents used for gravimetric methods tend to form

precipitates with groups of ions. In this sense they are

selective. Usually they do not form precipitates with a specific ion. This means that ions within a group interferes with the determination of any other ion in the group unless a

preliminary separation is performed.