HCl can maintain the quantitative precipitation.

HCl is added to ensure that the precipitate you obtain is more pure, which is that your precipitate obtained is less and bigger in size. Most precipitate is more soluble in acidic medium. So when HCl is added, the many small precipitate formed will dissolve back, and eventually slow the rate of precipitation which will favour the formation of bigger size precipitate. In gravimetric analysis, we need to add a precipitating agent in excess. Why do we do it? If we don't how will it affect the results? Best Answer - Chosen by Voters precipitating agent help the analyte (the compound you want measure it's weight) be participated almost completely. By adding precipitating agent the solubility of the analyte will get lower and the possibility of complete precipitation of the analyte will get higher. Excess precipitating agent will assure you the analyte is only in precipitation form and the amount of analyte in the aqueous form is minimum. For gravimetric analysis, you always need to add extra precipitating agent. Why? Because if you don't, there's going to be some reactants left over that you just don't want. More likely than not, labs pertaining to gravimetric analysis will ask you to find something about the limiting reagent. You can't really find anything about the limiting reagent if 1) you still have TWO or MORE reactants left over and 2) because you have some leftovers, you can't say which reactant is the excess or limiting in the first place. As mentioned before, it will screw your results. Hard. Because you don't have the amount of product that came out, you can't figure out how much of the limiting reagent you had to begin with. And because you don't have that, you can't figure out (theoretically) the exact amount of excess reagent that you use to react all of the limiting. And because you don't have that, lab grades go down the drain. Addition of excess precipitating agent to a solution of substances ensures that the required substance is completly reacting with the precipitating agent and that nothing is remained of the substance as unreacted. This gives a complete and accurate reaction. Otherwise, if the substance remains unreacted, due to insuffiecience of the reacting agent, then the results obtained may not be correct. The precipitate cannot be weighed with the necessary accuracy in place on the filter paper; nor can the precipitate be completely removed from the filter paper in order to weigh it. The precipitate can be carefully heated in a crucible until the filter paper has burned away; this leaves only the precipitate. (As the name suggests, "ashless" paper is used so that the precipitate is not contaminated with ash.) GRAVIMETRIC ANALYSIS Introduction Gravimetric analysis, which by definition is based upon the measurement of mass, can be generalized into two types; precipitation and volatilization. The quantitative determination of a substance by the precipitation method of gravimetric analysis involves isolation of an ion in solution by a precipitation reaction, filtering, washing the precipitate free of contaminants, conversion of the precipitate to a product of known composition, and finally weighing the precipitate and determining its mass by difference. From the mass and known composition of the precipitate, the amount of the original ion can be determined. Gravimetric methods are quantitative methods that are based upon determining the mass of a pure compound to which the analyte is related

For successful determinations the following criteria must be met: The desired substance must be completely precipitated. In most determinations the precipitate is of such low solubility that losses from dissolution are negligible. An additional factor is the "common ion" effect, this further reduces the solubility of the precipitate. When Cl- is precipitated out by addition of Ag+ Ag+ + ClAgCl(s)

The (low) solubility of AgCl is reduced still further by the excess of Ag+ which is added, pushing the equilibrium to the right. We can further decrease the solubility by decreasing the temperature of the solution by using an ice bath. The weighed form of the product should be of known composition. The product should be "pure" and easily filtered. It is usually difficult to obtain a product which is "pure", i.e. one which is free from impurities but careful precipitation and sufficient washinghelps reduce the level of impurity. Mechanism of Precipitation After the addition of the precipitating agent to the solution of the ion under analysis there is an initial induction period before nucleation occurs. This induction period may range from a very short time period to one which is relatively long, ranging from almost instantaneous to several minutes. After induction, nucleation occurs, here small aggregates or nuclei of Nucleation is a process in which a minimum number of atoms, ions, atoms form and it is from these "clumps" of atoms that the crystals which form the filtrate will grow. These nuclei may be composed of just a few atoms or molecules join together to give a stable solid. each so there may be up to 1010 of the nuclei per mole of precipitating product. As these nuclei form ions from the solution (which at this point are in excess) congregate around them. For example if hydrochloric acid were Adsorption is a process in which a added very slowly to a solution of silver nitrate, silver chloride nuclei would substance (gas, liquid, or solid) is form and silver ions (which would be in excess relative to Cl- ions) would held on the surface of a solid. In congregate around them. contrast, absorbtion involves the In addition to the primary adsorbed silver ion, there are some retention of a substance within the nitrate ions aggregating further from the AgCl nucleus. These are counter pores of a solid. ions and tend to aggregate around the [AgCl:Ag]+ center because these centers have a net positive charge (excess Ag+) and additional negative charge The electric double layer of a is required to maintain electrical neutrality. The counter ions are less tightly colloid held than the primary adsorbed ions and the counter ion layer is somewhat consists of a layer of charge diffuse and contains ions other than those of the counter ions. These layers of absorbed charges are known as the electric double layer. on the surface of the particles and a layer with a net opposite charge in the solution surrounding the particles A colloid is a solid made up of particles having diameters less than 10-4 cm. After nucleation growth occurs, large nuclei grow at the expense of smaller nuclei which dissolve. This process helps produce more easily filtered crystals (since it produces larger crystals).

Growth of larger nuclei or crystallites can be encouraged by digestion, a process which involves heating the solid and mother liquor for a certain period of time. During digestion, small particles dissolve and larger ones grow. Digestion of the product is an important practical process and you will find that most if not all gravimetric analysis involve a digestion period. Conditions for analytical precipitation A supersaturated solution is an unstable solution that contains more solutes than a saturated In an ideal world, an analytical precipitate for gravimetric analysis should consist of perfect crystals large enough to be easily washed and filtered. The solution. with time, supersaturation is relieved by precipitation perfect crystal would be free from impurities and be large enough so that it presented a minimum surface area onto which foreign ions could be adsorbed. of the excess solute. To increase The precipitate should also be "insoluble" (i.e. be of such slight solubility that the particle size of a precipitate, minimize the relative supersaturloses from dissolution would be minimal). ation during the precipitate Without going into detail, it has been shown (Von Weimarn) that the particle formation. size of precipitates is inversely proportional to the relative supersaturation of the solution during precipitation; relative supersaturation = (Q-S)/S For the best possible results, conditions need to be adjusted such that Q will be as low as possible and S will be relatively large. The following methods are used to approach these criteria, (we will employ the first); Precipitation from hot solution. The solubility S of precipitates increases with temperature and so an increase in S decreases the supersaturation. Precipitation from dilute solution. (We will employ this method next semester for the crystallization of a metal oxalate) This keeps Q low. Slow addition of precipitating reagent with effective stirring. This also keeps Q low, stirring prevents local high concentrations of the precipitating agent. Precipitation at a pH near the acidic end of the pH range in which the precipitate is quantitative. Many precipitates are more soluble at the lower (more acidic) pH values and so the rate of precipitation is slower. Digestion of the precipitate. (Also the digestion period results in some improvement in the internal perfection of the crystal structure [sometimes called ripening], here some internal foreign atoms may be expelled). Back To Top Impurities in Precipitates No discussion of gravimetric analysis would be complete without some discussion of the impurities which may be present in the precipitates. Coprecipitation Washing and Filtering This is anything unwanted which precipitates with the thing you do want. Coprecipitation occurs to some degree in every gravimetric analysis (especially barium sulfate and those involving hydrous oxides). You cannot avoid it - all you can do is minimize it by careful precipitation and thorough washing. Surface adsorption Here unwanted material is adsorbed onto the surface of the precipitate. Digestion of a precipitate reduces the amount of surface area and hence the area available for surface adsorption. Problems with coprecipitation and surface adsorption may be reduced by careful washing of the precipitate. With many precipitates, peptization occurs during washing. Here part of the precipitate reverts to the colloidal form e.g. AgCl(colloidal) AgCl(s)

This results in the loss of part of the

Washing can also remove surface material. Occlusion This is a type of coprecipitation in which impurities are trapped within the growing crystal. Postprecipitation

precipitate because the colloidal form may pass through on filtration. By washing with ice cold water this can be minimized Drying the solid

Generally the solids are dried at about 120oC but conditions for drying can vary considerably. To Sometimes a precipitate standing in contact with the mother liquor becomes contaminated by the precipitation of an impurity determine the correct drying regime, a thermogravimetric balance may be on top of the desired precipitate. used.