GRAVIMETRIC ANALYSIS

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

STEPS IN GRAVIMETRIC ANALYSIS

Preparation of the Sample Precipitation
sample

dissolved components

Digestion Calculation Calc lation Filtration and Washing W hi

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

How does precipitation occur?

1. As Ksp is exceeded, solution becomes supersaturated. Ag+ + ClKsp = [Ag+] [Cl-] / [AgCl] AgCl(s)

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

The Solubility of Precipitates

The solubility of a sparingly soluble electrolyte is characterized by its Solubility Product (Ksp). y y ( )
(Ksp the equilibrium constant for a reaction in which a solid dissociates into its ions)

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

Example: AgCl A Cl Ksp AgBr Ksp AgI Ksp

= 1 6 x10-10 1.6 10 10 = 7.7 x10-13 = 8.3 x 10-17

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

Predicting Precipitation Condition

When two solutions are mixed or when a compound is added to a solution, any one of the following condition may exist; the solution is, Unsaturated Saturated Supersaturated ( S d (precipitation begins) i i i b i )

A slightly soluble salt, MX contains M+ and X ions in aqueous solution. MX M+ + X-

The ion product, Q is the product of the concentrations of the ions at any moment in time; Q = [M+][X-]

14

The relationships between Q and Ksp are;

Q < Ksp: Q = Ksp: Q > Ksp :

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

Particle Size of Precipitates p

Colloidal suspensions
Tiny particles, invisible to the naked eyes (10-7 10-4 cm diameter) No tendency to settle from the solution Brownian motion prevents their settling out of the solution under the influence of gravity Colloidal suspensions are stable because all of colloidal particles are either positively or negatively charged because anions or cations are adsorbed on the surface of the particles Not easily filtered

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

Factors affecting particle size: gp

Precipitate solubility Temperature Reactant concentrations Rate of mixing the reactants

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

Von Weimarn equation

Growth of precipitates and crystals

e.g. sodium acetate crystals from a supersaturated solution p small particles and difficult to filter

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

Mechanism of Precipitate Formation a) Nucleation

A process in which a number of atoms, ions, or molecules j join together to give a stable solid, i.e. molecules in g g solution randomly form small aggregates of molecules Nucleation may also occur on the surface of suspended solid contaminants

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

Precipitates form by nucleation and particle growth p y p g

If nucleation predominates, a large number of very fine particles results If particle growth predominates, a smaller number of predominates larger particles is obtained If: Rate of Nucleation > Rate of Particle Growth then precipitate containing a large number of small particles. If: Rate of Nucleation < Rate of Particle Growth then precipitate containing a smaller number of larger p particles is produced. p Precipitates with large particle are more easily handled during filtration and washing washing.
23

How to Control Particle Size?

Elevate the temperature to increase solubility (S) of the precipitates, decreasing supersaturation Precipitate from dilute solutions (minimize Q), => volume of solution large, analyte and reagent concentrations are kept low Slow addition of the precipitating agent (to minimize Q) with good stirring to avoid localized supersaturation Precipitation from acidic solution. If the precipitate depends on pH, larger particle size can be obtained by controlling the pH. After the precipitate is formed, the particle size can be improved by digestion p ocess or by precipitation p oved d ges o process o p ec p o from homogeneous solution.
24

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

Why colloid suspensions are stable and do not coagulate spontaneously?

Particles of colloid are charged: either +ve or ve Due to cations or anions bound to (adsorbed on) the surface of the colloid particles e.g. Ag+ (or Cl-) on the surface of AgCl particle attracts anions (or cations) in the solution The electrical double layer on the colloid particles prevents particles from colliding and adhering

How do you p y prove that the colloid particles are charged? Observe their migration when placed in an electrical field

26

Adsorption of ions onto the colloidal surface:

The kind of ions retained on the surface of a colloidal particle , and their numbers depend on:
Lattice ions are more strongly held than others, e.g if AgNO3 is first added to a solution of containing Cl-, the colloidal particles of the precipitate are negatively charged due to adsorption of some excess Cl-. The charge becomes positive when excess of Ag+ is then added. The surface charge is minimum when the supernatant liquid contains an excess of neither ion.

When the concentration of the common ion becomes greater, the extent of adsorption (and thus the charge) of a particle increase rapidly
27

Precipitation of Silver Chloride (AgCl)

AgCl colloid particle in a solution contains an excess of AgNO3. Primary adsorption layer: attached directly to th t the solid surface lid f (Ag+) Counter-ion layer: excess of ve ions (NO3-) surrounding the charged particles to just balance the charge on the particle. particle Electrical double layer: primary adsorbed layer and the counterion layer
28

Precipitation Using an Electrolyte

Ionic compounds are usually precipitated in the presence of an electrolyte; for AgCl
The surface of the particle will have a small positive charge due to adsorption of excess silver ions. The ionic atmosphere surrounds the h h d h particle and has a slight net negative charge. For particle growth, colloidal particles must collide to coalesce. But the negative atmospheres around the particles repulse each other electrostatically. Adding electrolyte decreases the volume of the i i t th ionic atmospheres, allowing h ll i repulsion to be overcome.

In the concentrated AgNO3:

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

In the diluted AgNO3:

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.

Increase the electrolyte concentration y

The concentration of counter-ions increases in the vicinity of each particle, The volume of the solution that contains sufficient counter-ions to balance the charge of the primary adsorption layer decreases. Adding electrolyte shrinks the counter-ion layer, the particles can approach counter ion layer one another more closely and agglomerate.
31

Properties of Precipitates and Precipitating Agents

Gravimetric G i t i precipitating agent should i it ti t h ld
React specifically or selectively React with the analyte to give product that is easily easil filtered and washed free of contaminants ashed of low solubility no significant loss of the analyte occurs during filtration and washing unreactive with the constituents of the atmosphere of known chemical composition after it is dried, or ignited. Example of selective reagent: AgNO3: precipitates from acidic solution, Cl-, Br-, I-, and SCN Example of specific reagent: Dimethylglyoxime: specifically precipitates Ni2+ from alkaline solution

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

Common Inorganic Precipitants

Precipitant NH4OH Analyte Al Fe HCl AgNO3 NaSO4 BaCl2 Ag Cl Ba SO42Precipitate Formed Al(OH)3 Fe(OH)3 AgCl AgCl BaSO4 BaSO4 Precipitate weighed g Al2O3 Fe2O3 AgCl AgCl BaSO4 BaSO4
34

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

Aluminium ion can be precipitated at pH 4. A higher pH is required to precipitate magnesium.

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