Analytical Chem.

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Introduction1

-Analytical chemistry could be divided into three main parts; qualitative, quantitative & applied. -A course of qualitative analysis is required in the programs of future chemists, pharmacists, premedical students, and many others.

-As the term implies, qualitative analysis deals with detection and identification of different substances singly or in a mixture.
-It is assumed that student after this course will be familiar with the operations; colour reactions, precipitation, filtration, evaporation, flame tests, ignition tests and semimicro analytical operations. -This part deals with the qualitative analysis of anions, which could be defined as the negatively charged fragments of salt or compound or acid radical.

An example is Nacl:
NaCl Na + + Cation Basic radical ClAnion Acid radical
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Qualitative Analytical Chemistry

Methods of qualitative analysis are: (1) Simple: where identification of a single compound in pure state takes place.

(2) Complicated: where identification of a mixture of substances takes place by: a. simple chemical separation Or b. advanced instrumental techniques
Chemical Reactions The identification of a substance involves its conversion usually with the aid of another substance of known composition into new compound possess characteristic properties. This transformation is called: Chemical Reaction The substance by which this transformation occurs is called Reagent

-Solute Solvent

Solution

-Dilute soln: has a relatively smaller proportions of solute to solvent -Concentrated soln: has a relatively large proportions of solute to solvent

-Unsaturated soln: the solution which contains less solute than required according to its solubility

-Saturated solution: there is a limited amount of solute that can dissolve in a given amount of solvent at particular temperature
-Supersaturated soln: in which there is more solute than required for saturation

-Solubility: the concentration of a saturated soln of any substance measured at const. tem

-According to the solute state, we can classify the reactions into: (1) Dry reaction: done on solid solute (2) Wet reaction: done on soln of solute (more rapid) -In aqueous solutions, most acids, bases and salts are ionized, so reaction is called: ionic reaction -Mechanism of ionic reaction: (1) As a result of combination of ions or of ions and molecules (2) As a result of electrons transfer Fe2+ -e Fe3+ (oxidation= loss of electrons) This is known as oxidation-reduction reaction (redox reaction) Types of chemical reactions: (1) Acid-Base or neutralization reaction acid + base salt+H2O Acid: substance which gives proton or loses proton and the resulting fragment is called: conjugate base

Base: substance which accepts proton and the resulting fragment is called: conjugate acid

(2) Complex forming reactions: many anions and molecules are able to use their lone pair of electrons (e.g. N, O, CN,..called: ligands) to coordinate with a metal ion. Ligandelectron donor metal.electron acceptor

(3) Polymerization reactions: many chemical species are capable of reacting in aqueous solution with like species to form chains or rings, this process is called: Polymerization, It is prevalent among oxy anions as phosphae, molbydate, vanadate, chromate & periodat -Two or more species may combine to form mixed polymer. (4) Redox reactions: which involve change in the oxidation state of the reactants by transfer of electrons Ce 4+ + Fe 2+ Ce 3+ + Fe 3+ (5) Precipitation reactions: where formation of a solid phase from a reaction in solution occurs. Precipitation may occur due to: 1. Simple ionic interactions as formation of barium sulfate Ba2+ + SO42BaSO4(s) 2.Reaction of ions with organic compounds as pptn of nickel with dimethylglycoxime (6) Volatilization reactions: formation of a gas or vapour as release of CO2 on acidification of carbonate soln: Na2CO3 + 2HCl 2NaCl + CO2 + H2O 6

Chemical Equations

Three kinds of equations may be written: (1) Molecular (2) Detailed (3) Net equations
1. Molecular Equations: e.g. neutralization of HCl with NaOH HCl + NaOH NaCl + H2O

-Of course these substances arent molecules but these equations dont indicate the presence of ions. -They represent the exact stoichiometry of the reaction (1mole of acid reacts with one mole of base) - They enable us to calculate how many grams of solid NaOH would have to be dissolved in water in order to give a solution that would exactly neutralise an acidic soln which is prepared by a definite number of grams of HCl gas in water. -but not tell us anything about the mechanism of the reaction
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2. Detailed Equations or Ionic Equations: -more accurate representation of the reaction as it actually occurs. -they describe what happens to solutes when they are dissolved in water. -based on the previous example (HCl neutralizes NaOH), any strong electrolyte is completely ionized once present in soln even dilute one. - So there are no more molecules, ions will react: Na+ + OH- + H+ + ClNa+ + Cl- + H2O (weak electrolyte)

3. Net Equations: -if you examine the above detailed eqn, you will find that Na+ & Cl- ions do not actually undergo any change, i.e. the same Na+ & Cl- ions are present in reactants as in products (no change), so we can cancel them from both sides. OH- + H+ H2O -The net eqn is useful as it focuses our attention on the changes that actually occur during a reaction

-How the eqns will be for: NH4OH + HCl

NH4Cl + H2O???

-NH4OH is a weak electrolyte so a part will be dissociated into ions and the rest will be undissociated Molecular eqn: NH4OH + HCl Detailed eqns: (a) NH4OH (b) H+ + Cl- + OHNH4Cl + H2O NH4+ + OHH2O + Cl-

or

NH4OH H+ + Cl- + NH4+ + Cl- + H2O NH4+ + OH-

Net eqn:

NH4OH + H+ (weak electro.)

NH4+ + H2O

Exercise: -What will happen for: PbCl2 + H2S gas (weak electrolyte)?

-What will happen for: CaCO3(insoluble) + 2HCl?

Rules: 1.The following soluble compounds being strong electrolytes: a) All soluble salts b) All soluble metal hydroxides c) Common acids (HCl, H2SO4, HNO3, HI, HBr.)

2. The following soluble compounds being weak electrolytes: a) NH4OH b) Water c) All soluble acids other than previously mentioned (acetic acid, Phosphoric acid, boric acid.)
3. All insoluble substances exist as molecules or neutral ions (CuS, CaCO3, PbSO4)

4. Complex ions are soluble weak electrolytes and exist predominantly as undissociated ions e.g. ferrocyanide [Fe(CN)6]4Exercise: Write the net equation for each of the following: 1. 2. 3. 4. Reaction of NH4OH with FeCl3 Dissolving of solid ZnS by xss HCl Reaction of NH4OH and CH3COOH (acetic acid) Dissolving ppt of AgCl in NH4OH soln

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Chemical Equilibria
-All ionic reactions may be considered to be reversible to some degree i.e. they proceed in two opposing directions at the same time.
-One proceeding towards the products and the other towards the recombination of the products to produce the initial reactants. -If the external conditions of the system undergo no change, the rates at which the two opposing reactions progress will become equal, such a condition is said to be: a state of equilibrium.

-But this equilibrium is dynamic, implying the two opposing reactions are still in progress.
Law of Mass Action: (applied only for weak elctrolytes & sparingly sol. sub.) -The rate of a chemical reaction is proportional to the active massess of the reacting substances present at the time. -Active mass is usually expressed in molar conc aA+bB cC+dD rateforward= Kf [A] a [B] b ratereverse= Kr [C] c [D] d
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At equilibrium: ratef = rater

Ke = Kf/Kr = [C]c [D]d / [A]a [B]b

Ke is known as equilibrium constant, its numerical values indicate the position of equil.

Ke > 1, so Kf > Kr and the rate of forward reaction is higher.

Ke varies with temperature. Principle of le Chtelier: states that: when a stress is applied to a system in equil., the equilibrium will shift in such a manner as to relieve or neutralize the stress Factors affecting the equilibrium: (1)Temperature: increasing the temp. always favors the endothermic change, and decreasing the temp. always favors the exothermic change. (2) Pressure: increasing the pressure causes a shift in the direction that will decrease the number of moles of gas, so decrease the volume. N2(g) + 3H2(g) H2(g) + I2(g) 2NH3(g) causes the equil. to shift to the right. 2HI(g) is there a shift in equil.?

(3) Concentration: if the conc of a substance is increased, the equil. will shift in a way that will decrease the conc of the substance that was added.
12 H2 + I2 2HI increase H2 or I2 shift to formation of HI, while removal of them, shift to decomposition of HI

VOGELs Qualitative Inorganic Analysis 7th Edition 1996

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