Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Quantitative method based upon measuring the mass of a pure compound to which the analyte is chemically related.
Two types of gravimetric methods: 1. Precipitation method y p p - based on determination of an analyte which is precipitated by a reagent. -the precipitate is a slightly soluble substance with a known composition or - it can be converted to one of known composition. 1
Eg.1: determination of Cl by the addition of Ag+ to form AgCl; Ag+ + Cl AgCl (S) Eg.2: precipitation of Fe (III) as Fe (III) hydroxide. The hydroxide will be converted to weighable oxide. The precipitated form and weighed forms are not be the same compound. Fe3+ + 3NH3 + (x+3)H2O Fe(OH)3.xH2O(s) + 3NH4+
,1000oC
2Fe(OH)3.xH2O(s) Fe2O3(s) + (2x + 3)H2O
2
2. 2 Volatilization methods - for determination of volatile components (H2O, CO2, etc.) of a sample. - The sample is warmed or ignited and the amount of the component is found from the loss in mass of p the sample. Or, volatile components can be absorbed by a suitable absorbent. The amount of the components are found from the increase in the weight of the absorbent.
3
dissolved components
precipitating agent
Weighing
Drying or Ignition
Preparation of the solution Solid sample must be dissolved in a suitable solvent. Some form of preliminary separation may be necessary to eliminate interfering materials. g Requirements for Precipitate low solubility solubility. the precipitate in a form suitable for filtration. Proper adjustment of the solution condition may also mask potential i i l interferences. f
Factors that Must be Considered when Preparing the Solution
Volume of th solution d i precipitation. Vl f the l ti during i it ti Concentration range of the test substance. The presence and concentrations of other constituents. Temperature pH
Precipitation Process
Ideally, wed like a precipitate that forms quickly. This implies:
Large, pure crystals Low solubility Easily filtered Easily washed Analyte + Precipitating Agent y p g g Supersaturation Precipitation
p g ( p 2 At some point nucleation begins. (Nucleation - a process involving formation of very small aggregates of a precipitating solid. 3. At the same time, crystal growth begins. (Crystal growth formation of larger particles of a precipitating solid by deposition of ions/molecules i / l l on the surface of existing nuclei. h f f i i l i
6
Example:
AgCl, is a slightly soluble salt. The solubility equilibrium can be represented as; AgCl(s) Ag+ (aq) + Cl- (aq) Ksp = [Ag+][Cl-]
The solubility product (Ksp) of a compound is used as a measure of the y p ( p solubility of sparingly soluble salt. For compounds which have similar formula, the smaller Ksp, the less soluble p the compound.
7
The solubility product constant of AgI is smaller than AgBr and AgCl. It means that the solubility of the AgI is smaller than the others. But when comparing salts of different valence type, the order may be different. y p p p g Solubility product expressions for more complex formulas are given as below;
MgF2(s) Ag2C03(s) Ca3(PO4)2(s) Mg2+(aq) + 2F-(aq) 2Ag+(aq) + CO32-(aq) 3Ca2+(aq) + 2PO43-(aq) Ksp = [Mg2+][F-]2 Ksp = [Ag+]2[CO32-] Ksp = [Ca2+]3[PO43-]2
8
Example: Calculate the solubility of AgCl in a saturated solution of AgCl if Ksp of AgCl at 25 oC is 1.0 x 10-10. When AgCl ionizes, equal amounts of Ag+ and Cl- are formed. Let say, s is molar solubility of AgCl. AgCl A Cl(s) Ag A + (aq) + Cl- (aq) x x
Ksp = [Ag+][Cl-] = (x) (x) x2 = 1.0 x 10-10 x = 1.0 x 10-10 = 1.0 x 10-5 M So, So the solubility of AgCl is 1.0 x 10-5 M 10
9
Example: Which has greater solubility in water: 8 12 AgIO A IO3 (Ksp = 3 0 x 10-8) or L (IO3)3 (Ksp= 6 5 x 10-12) ? 3.0 La(IO 6.5 Ag+ + IO3x x Ksp = [Ag+][ IO3-] = 3.0 x 10-8 [Ag+] = [ IO3-] = x (x) (x) = 3.0 x 10-8 x = 3.0 x 10-8 = 1.73 x 10-4 mol L-1 AgIO3 La(IO3)3 ( La3+ + x 3IO33x
(x) (3x)3 = 6.5 x 10-12 [La3+] [IO3- ]3 = 6.5 x 10-12 27x4 = 6 5 x 10-12 6.5 x = 46.5 x 10-12/27 = 7.0 x 10-4 mol L-1 The Ksp for AgIO3 is greater than that for La(IO3)3, but La(IO3)3 is more g g ( ( soluble.
10
Effect of pH on Completeness of Precipitation pH of solution influences the degree of precipitation. Example: Mg(OH)2(s) Mg2+(aq) + 2OH-(aq)
Adding OH- ions (increasing the pH) shifts the equilibrium from right to left, thereby increasing the precipitation (decreasing the solubility) of Mg(OH)2. Adding H+ ions (decreasing the pH) shifts the equilibrium from left to right and the solubility of Mg(OH)2 increases.
11
Example: At what pH will Al(OH)3 begin to precipitate from p ( ) g p p 0.10 M AlCl3 The equilibrium is; Al(OH)3 Al3+ + 3OH-
[Al3+][OH-]3 = Ksp (0.1) [OH-]3 = 2 x 10-23 [OH-] = 32 x 10-23/0.1 = 5.848 x 10-8 M p pOH = -log [5.848 x 10-8 ] = 7.23 g[ pH = 14 7.23 = 6.77 The aluminium hydroxide precipitates when the pH just exceeds 6.77.
12
Effect of Temperature on Completeness of Precipitation The solubility product depends on temperature. If the temperature alters, the solubility product of the p , yp precipitate also changes. For example, the solubility of AgCl at 100oC is nearly example 25 times as high as at 10oC. But B some precipitate lik B SO4, the solubility only i i like BaSO h l bili l doubled when the temperature is raised from 10oC to 100oC. In some instances the solubility of precipitate decreases with rise of temperature temperature.
13
The ion product, Q is the product of the concentrations of the ions at any moment in time; Q = [M+][X-]
14
Unsaturated solution Saturated solution (the system is at equilibrium) Supersaturated solution; MX will precipitate until the product of th i i d t f the ionic concentrations is equal to Ksp
Precipitation occurred when the ion product exceeds Ksp for that substance.
15
Effect of Common Ion on Precipitate The condition of precipitation can also be affected by adding more of any of the precipitating ions. Example: If a solution is saturated with barium sulfate, BaSO4(s) Ba2+ + SO42-, Ksp = 9.12 x10-11
If, more sulfate or Ba2+ is added to the solution, the reaction will shift to the left ( more precipitate formed). This effect is called the common ion effect.
16
Example: E l Calculate the molar solubility of lead iodide; (a) in water, (b) in 0.20 M NaI solution. The Ksp for PbI2 is 7.9 x 10-9. (a) The equilibrium is; PbI2 Pb2+ + 2Is 2s for which Ksp = [Pb2+] [ I- ]2 p (s) (2s)2 = 7.9 x 10-9 4s3 = 7.9 x 10-9 solubility = s = 1.3 x 10-3 M
17
(b) The same equilibrium expression holds: Ksp = [Pb2+] [ I- ]2 Two T sources of iodide: the NaI and PbI2. Th amount of f i did th N I d The t f iodide coming from the PbI2 is small compared to that from the NaI. Thus, [ I- ] = x + 0 2 0 2 0.2 0.2 Then, [Pb2+] = solubility = Ksp /[ I- ]2 p = 7.9 x 10-9/(0.20)2 = 2.0 x 10-7 M The solubility has decreased upon addition of an excess of I-.
18
Colloidal suspensions appear clear and contain no solid but because solid, particles of colloidal suspensions scatter visible light, the path of the beam can be seen by the eye. This phenomenon is called Tyndall effect.
Crystalline suspensions
Larger particles (tenth of a mm or greater) p y Settle spontaneously Easily filtered
19
Relative supersaturation
Q-S Relative supersaturation (RSS) = S Q = the concentration of the solute S = equilibrium solubility of the solute
Particle size of a precipitate varies inversely with the relative supersaturation during mixing of reactants. When (Q S)/S is large small precipitate size When (Q S)/S is small larger precipitate size
20
In gravimetric analysis we minimize the supersaturation in p order to obtain larger and easily filterable solid particles In a supersaturated solution, nucleation goes faster than particle growth. This is bad because you wind up with many small particles in solution (a colloid) and few large ones Must do M t d something to promote particle growth thi t t ti l th
21
Supersaturated Solution
Unstable solution that contains a higher solute concentration than a saturated solution By time, the excess solute will precipitates out of the supersaturated solution d l i
b)
Particle Growth
After nucleation, further precipitation takes place on the existing nuclei, i.e. particle growth. nuclei i e growth i.e. the addition of more molecules to the aggregate to form a crystal
22
Colloidal P i i C ll id l Precipitates
A colloidal precipitates is formed when a precipitate has a low solubility: S <<< Q, because relative supersaturation remains high throughout the precipitation process. Example of colloidal precipitates (because of their very low solubilities): ) hydrous oxide of iron(III), aluminum, and chromium(III) Sulfides of most heavy metal ions
25
How do you p y prove that the colloid particles are charged? Observe their migration when placed in an electrical field
26
When the concentration of the common ion becomes greater, the extent of adsorption (and thus the charge) of a particle increase rapidly
27
the effective charge on the particles prevents them from approaching one another more closely than 2d1 a distance that is too great for coagulation to occur
The two particles can approach within 2d2 of one another. As the AgNO3 becomes more diluted, the distance between , particles becomes small enough for the forces of coagulation to take effect and coagulated precipitate to appear. 30
Coagulation of Colloids g
We can coagulate or agglomerate individual particles of most colloids to give a filterable, amorphous mass that g , p settle out of solution Coagulation can be hastened by heating, by stirring, and by adding an electrolyte to the medium. medium Heating
Decreases the number of adsorbed ions, and thus the thickness of the double layer The particles gain kinetic energy at higher temperature to overcome the barrier to close approach posed by the double layer.
32
Inorganic Precipitants g p Form slightly soluble salts or hydrous oxides with the anal te ith analyte. Most inorganic reagents are not very selective. Two T o common inorganic precipitating agents are, silver nitrate which is used to precipitate nitrate, halide ions such as chloride, barium chloride, which is used to chloride precipitate sulfate ion.
33
Organic Precipitants
Very useful precipitating agents for metals. Advantages by using organic reagents as a precipitant ; It forms chelate compounds with cations which are very I f h l d ih i hi h insoluble in water. So, that metal ions may be quantitatively p precipitated. p The organic precipitant often has a large molecular weight. Thus a small amount of metal may yield a large weight of precipitate. precipitate Some of the organic reagents are fairly selective, yielding precipitates with only a limited number of cation. By controlling such f t t lli h factors as pH and th concentration of H d the t ti f masking reagents, the selectivity of an organic reagent can be enhanced. The precipitates obtained with organic reagents are often 35 coarse and bulky, and hence easily handle.
Examples: 8- hydroxyquinoline (oxine) It can precipitates many elements but can be used for group separation by controlling pH.
O
2 N .. OH
Mg2+ N
O Mg Mg N
+ H+
36
Dimethyglyoxime is, Principally used for determination of nickel. The reaction Ni2+ + 2C4H8N2O2 Dimethyglyoxime Ni(C4H7N2O2)2 (p) + 2H+
This precipitate is so bulky that only small amount of nickel can be handled conveniently.
37