G.L.A. UNIVERSITY MATHURA NAME PHARMACEUTICAL ANALYSIS CORSE YEAR Submitted from : Submitted to : Ashu Mr. P K Upadhyaya sir1) A) Law of mass action :: ~-> The law of mass action is derived by C.M. Guldberg and Peter Waage in 1867. —-> According to the law of mass action "The rate at which a substance reacts is directly proportional to its active mass and the rate of chemical reaction is directly proportional to the product of active mass of the reactant.” --> The term "Active mass" represents the molecular concentration. > The research performed by C.M. Guldberg and Peter Waage between 1864 and 1879 in which equilibrium constants were derived by using kinetic data and the rate equation which they had proposed. Guldberg and Waage also recognized that chemical equilibrium is a dynamic process in which rates of reaction for the forward and backward reactions must be equal at chemical equilibrium.. In order to derive the expression of the equilibrium constant appealing to kinetics, the expression of the rate equation must be used. The expression of the rate equations was rediscovered later independently by Jacobus Henricus Van't Haff. |B) Derivation of law of mass action :: aA+bB 2 cc+dDd According to the law of mass action : Rate of forward reaction (Ra) & aj?” Ra = x1 (Ai?(0)” Similarly = Rate of reverse reaction (R2) « [C]¢ [D]? R2 = K2 [C}* [D]* Where, K1 and K2 are the proportionality constants for forward and backward reactions, respectively Rate of forward reaction = Rate of backward reaction ki ate? = Ke (CF (DF (cs (0}" Keq ne? rium constant. Where Kea = Eq 2) A) Common lon Effect :- -> According to the common ion effect "The decrease in ionisation of a weak electrolyte by addition of a strong electrolyte having an ion common with the weak electrolyte is known as \common ion effect."‘The common ion effect is responsible for the reduction in the solubility of an ionic precipitate when {a soluble compound containing one of the ions of the precipitate is added to the solution in equilibrium ith the precipitate. It states that if the concentration of any one of the ions is increased, then, accordingto Le Chaterlier's principle some of the ions in excess should be removed from solution, by combining with the oppositely charged ions. Some of the salt will be precipitated until the ion product is equal to the solubility product. Examples of common ion effect :- Example 1: lonization of acetic acid is suppressed by addition of sodium acetate - CHsCOOH = + H+ CHsCOONa = + Nat |-> The concentration of H+ ions produced is low which causes only pH up to acidic (the mixture of these in acidicbuffers.) Example 2:- Ionization of ammonium hydroxide is suppressed by the addition of ammonium chloride - NHsOH = +oH NH = +a- |-> The concentration of 0-H ions produced is low which causes only pH to basic (the Imixture of these in basic buffers.) B) Derivation of common ion effect |-> Consider a weak electrolyte AB, ionized in the solution, as- AB & At +B Applying law of mass action :- [a+] [8+] [AB] |> Suppose, AD is added to the AB electrolyte solution, having an ion common to that lelectrolyte. Following equilibrium will exist in the solution. (Weak) AB = +B (Strong) AD= +D- 3) A) Ostwald dilution law :- '--> According to the Ostwald dilution law "For a weak electrolyte, the degree of ionization is inversely proportional to the square root of molar concentration or directly proportional to the Isquare root of volume containing one mole of the solute,”B) Derivation of Ostwald dilution law :- -> The law is only applicable to weak electrolytes. It can be applied to acetic acid or ammonium hydroxide in aqueous solution. HCOOH + H20 2 Hs0+ + CHsCOO- NHaOH + H20 2 Nat + OH Consider a general equilibrium for a weak acid :- HA + 120 2 HsO+ + AW [H30-] is actually [Hs], on simplification it gives :- H20 HA SOW +A imole 0 0 tially) od « « _(at equilibrium) K [120] =Ka= A) [HA] Where, Ka = dissociation constant of the acid. In general, K = dissociation constant of any weak electrolyte -> When electrolyte is dissociate in one gram equivalent upon dilution. Therefore, 1 ve oe c Where C If, ccis the degree of dissociation at equilibrium, then the amount of undissociated electrolyte will bbe (1-) gram equivalent ‘Therefore, undissociated dectrolyte= (1- 0) /V (weakacid ) Concentration of each ion = « Applying law of mass action putting in the equation 1) :- or 2)~-> This is known as Ostwald's dilution law because the dissociation constant is expressed in erm of dilution or volume. In case of weak electrolyte = «<< 1 ( For weak acid) Hence, dec ~ 1 unity) since V=1/C) C) Limitations :- [The cause of failure of Ostwald's dilution law in the case of strong electrolytes is due to the following \ctors = (1) The law is based on the fact that only a portion of the electrolyte is dissociated into ions at lordinary dilution and completely at infinite dilution. strong electrolytes are almost completely ionized at all dilutions and A/Aee does not give accurate value of ‘a’. (2) When concentration of the ions is very high, the presence of charges on the ions appreciably leffects the equilibrium. Hence, law of mass action in its simple form cannot be strictly applied in the case of strong electrolytes. 4) A) lonization:- |-> lonization is the process by which an atom or a molecule acqi icharge by gaining or losing electrons to form ions, often in conjunction with other chemical ichanges. lonization can result from the loss of an electron after collisions with subatomic particles, collisions with other atoms, molecules and ions, or through the interaction with light. lHeterolytic bond cleavage and heterolytic substitution reaction can result in the formation of ion pairs. lonization can occur through radioactive decay by the internal conversion process, in hich an excited nucleus transfers its energy to one of the inner shell electron causing it to be lejected. B) Uses:- everyday examples of gas ionization are such as within a flourescent lamp or other electric discharge lamps. It is also used in radiation detectors such as the Geiger Muller counter or the ionization chamber. iThe ionization process is widely used in a variety of equipment in fundamental science and in such as Imass spectroscopy and radiotherapy.