UNIT 14 ELECTROLYTIC CONDUCTION

Structure
14.1 Introduction
Objectives

14.2 Electrolysis 14.3 Comparison of Galvanic and Electrolytic Cells 14.4 Faraday's Laws of Electrolysis and Electrolytic Conduction 14.5 Measurement of Conductance of Aqueous Solutions of Electrolytes 14.6 Results of Conductance Measurements and their Interpretation 14.7 Kohlrausch's Law and its Usefulness 14.8 Conductometric Titrations 14.9 Acids and Bases 14.10 Acid-Base Equilibria 14.11 Common Ion Effect 14.12 Acidity and Alkalinity of Aqueous Solutions 14.13 Buffer Solutions and Hydrolysis 14.14 Hydrolytic Equilibria 14.15 Precipitation Equilibria 14.16 Applications of the Solubility Product
14.16.1 Solubility and IGp 14.16.2 The Effect of Added Electrolytes 14.16.3 Applications in Qualitative Analysis

14.17 Summary 14.18 Glossary 14.19 Answers to SAQs

14.1 INTRODUCTION
In the previous unit, sources of electrical energy like the primary and secondary cells were discussed. Electrical energy can be transported through matter by the conduction qf electric charge from one point to another in the form of an electric current. This can take place if there are charge carriers in the matter. These charge carriers can be electrons, positive ions and /or negative ions. Substances like diamond, silica etc., ujhich offer high resistance to the flow of electric charge are called insulators. Metals like copper, silver etc. which offer very little resistance to the passage of electricity are called conductors. The conduction in metals is referred to as metallic or eltctronic condition since the electrons of the metal are able to migrate freely and carry the negative charges through the metal. A inetal can be . considered to be a rigid lattice of positive ions around which are smeared an equal number of mobile electrons. On applying an electrical potential, the electrons are forced to move in one direction while the positive ions remain stationary. The electronic conduction. however, decreases with an increase of temperature as a consequence of an increase in the thermal vibrations of the lattice. In the case of semiconductors like silicon, germanium etc., the electronic conduction increases with an increase of temperature. The electrons, rather tightly bound to local centres at room temperature, become free to move as the temperature is increased. Both the conductors have one common characteristic, i.e., there is no chemical change accompanying the charge transport.

Equiiibria

-demW

Objectives
After studying this unit, you should be able to : * use Faraday's laws of electrolysis to calculate the amounts of material deposited or dissolved,

* predict the electrode reactions in electrolytic cells, * differentiate between galvanic and electrolytic cells. * explain the dependence of conductance of strong and weak electrolytes on
concentration,

* appreciate the usefulness and applications of conductometric titrations, * define acids and bases,. * calculate the pH of solutions of acids or bases, * apply the Henderson equation to calculate the pH of buffer solutions, * explain how salts can be acidic or basic using hydrolytic equilibria, and * appreciate the usefulness of the solubility product principle in qualitative
analysis.

14.2 ELECTROLYSIS
Electrolytes like sodium chloride, either in the molten state or in an aqueous solution conduct electricity but are decomposed by the passage of an electric current. A current of electricity can be passed into an aqueous solution or a fused salt via two electrodes dipping into the solution. The electrode connected to the negative pole of the battery is a source of electrons and is the cathode of the electrolytic cell, since reduction can occur at this eleceode. The other electrode connected to the positive pole of the battery is deficient in electrons and so can accept electrons. It is the anode of the electrolytic cell. Under the influence of an applied EMF the positive ions (cations) of the electrolyte move towards the cathode and get reduced. The negative ions(anions) move towards the anode and get oxidised. This movement of ions of an electrolyte under the influence of an applied EMF is called electrolytic conduction and its chemical decomposition caused by the passage of electricity is called electrolysis. As a specific example. we consider the electrolysis of molten sodium chloride using inert electrodes like Pt or graphite that do not react with either the electrolyte or the products of electrolysis. Of the two ions present, Na+ and C1-, only the Na+can be reduced. At the cathode of the electrolysis cell, the reduction reaction, Na+ ( 1 ) + e- = Na ( 1 ), occurs and the sodium metal collects around the electrode. The C1- anion on reaching the anode, loses the electron (oxidation) to the anode and a neutral chlorine atom is formed. Two such atoms combine to give a chlorine molecule, which bubbles off as a gas. The net chemical change that takes place in the electrolytic cell is called the cell reaction. It is obtained by adding together the anode and cathode reactions in such a way that the same number of electrons are gained and lost. Thus, in the electrolysis of molten NaCl, cathode reaction : 2Na'+2e-=2Na anode reaction : Cell reaction : 2Clm- 2 e=C12 2 Na + CI,

2 Na++2 Cl-->

(electrolysis) In the simple case of molten sodium chloride, the current-carrying ions are found to get discharged at the electrodes. When many electro-active species (capable of getting reduced or oxidised at the electrode) are present and also the electrode material is susceptible to be attacked, complications arise. Reactions of several types are possible at each electrode. The reactions that may occur at the anode include i) dissolution of the anode by oxidation e.g., Ag--> Ag' + e- ;Cu > cu2++ 2 e-, etc.

ii) discharge of anions, and e.g., 2 Cl- --+ C12+ 2 e'} iii) oxidation of water in aqueous solutions

EleclrdytlcConduction

Among the conceivable oxidation reactions at the anode, the reaction with the more negative (less positive) reduction potential is likely to take place. If the applied EMF is gradually increased, the oxidation process occur in the order of increasing reduction potentials (most negative first and least negative last). After all, this is a prediction based on thermodynamics and so one should actually know how rapid these electrode processes are in order to predict the electrode reaction. At the cathode, reduction of a cation to give metal takes place in a few cases. Ag++ e ' j Ag In the case of cations of highly reactive metals like Na, K.etc., it is water that is preferentially reduced to give hydrogen

Examples :
(1)

Electrolysis of an aqueous solution of Na Cl- - using Pt electrodes

+

Cathode Reactions Na++e =Na

Remarks Not possible because of negative EO value possible. Products at the cathode are H2 and OH-. Na+ ions move towards the. cathode to preserve elecmcal neutrality. Concentration of Wis too small for this reaction to occur

Anode Reaction 2C1--2e=C12(g) 240->02+4W+4e-

Remarks Actually observed Oxygen evolution is not observed

H2 ( g ) + C12( g ) + 2 O K Therefore, the net Cell Reaction : 2 C1- + 2 H, 0 -> ' electrolysis (2) Electrolysis of an aqueous solution of sodium sulphate using Pt electrodes to give hydrogen at the cathode and oxygen at the anode : Cathode: Anode : Therefore, the cell reaction is 2H20+2em=H2(g) +20H2H2O=O2(g) + 4 H + + 4 e -

If the H+and O H ions are allowed to mix, the cell reaction will be

What is the function of sodium sulphate in this case? The anode reaction results in the formation of H+in the anode. The sulphate anions migrate to the anode to maintain electrical neutrality. Simil'arly positive ions ( Na') move into the cathode region to

compensate for the presence of O H ions. It will be noticed that the current-carrying ions need not necessarily be discharged at the electrode. The ability to carry current depends on the concentration and speeds of the ionic species. But the ability to get reduced or oxidised depends on the electrode potential.

14.3 COMPARISON OF GALVANIC AND ELECTROLYTIC CELLS

In a galvanic cell, electrons released during oxidation at the anode push the electrons
of L h e anode material into the external circuit. The anode, being a source of negative charge, is the negative electrode. At the cathode, electrons are used up for the reduction reaction and as a result of the electron deficiency it is called the positive electrode. In electrochemistry. electrodes are designated as anode or cathode depending on whether oxidation or reduction takes place at an electrode. In an electrolytic cell, the anode is the positive electrode since it is connected to the positive pole of the galvanic cell. Anions attracted by the anode, get oxidised and the electrons released to the anode are drawn by the cathode of the galvanic e l l to be used in the reduction reaction in the galvanic cell. The cathode of an electrolytic cell is a negative electrode since it is comected to the negative pole (anode) of the galvanic e l l . The electrons released during the oxidation at the anode of the galvanic cell are available for the reduction of catiws or other species at the cathode of an electrolytic cell. Thus the galvanic cell may b& linked to an electron-circulating pump, taking electrons from the anode to the cathode of an electrolysis cell (Figure 14.1).

Galvanic

Electrolysir cell

Figure 14.1 :Galvanic and E l e d y s i s cells

14.4 FARADAY'S LAWS OF ELECTROLYSIS AND ELECTROLYTIC CONDUCTION

-

p -

--

Michael Faraday was the first to describe quantitatively the ralationship between the quantity of electricity passed (current in ampere x time in seconds or amp. sec or coulombs and the extent of chemical decomposition brought about by electrolysis. His investigations are sumrnarised in the form of two laws of electrolysis.

First law : The amount of any substance deposited at or dissolved from an

electrode as a result of the passage of an electric current is proportional to the quantity of electricity passed.

If W grams of a substance are deposited or dissolved by passing a current of i -amperes for t seconds, according to the first law

In Eqn. 14.1, e is called the electrochemical equivalent of the substance. From Eqn. 14.1, it is seen that when i t or the quantity of electricity passed is one coulomb, W = e. Thus, the weight of the substance deposited or dissolved by the passage of one coulomb of electricity is the electrochemical equivalent, It is no longer used.

Second Law :The masses of different species deposited at or dissolved from electrodes by the same quantity of electricity are proportional to their chemical equivalent weights.
I f W, and W2 are the amounts of two products of electrolysis obtained by passing q Coulombs of electricity, according to the second law

In Eq. 14.2, E, and E2 are the chemical equivalent weights of substances 1 and 2 respectively. Equations 14.1 and 14.2 can be combined to give Eqn. 14.3

In Eqn. 14.3, F is a constant of proportionality. It will be seen that W = E when i t = F. In other words F, called the Faraday, is the quantity of electricity required to deposit or dissolve 1 gram equivalant of a substance. The value of F has been found to be 9.6487 x 184 C/mol of electrons or 96500 C/mol of electrons. The equivalent weight is equal to the molecular or atomic mass divided by the number or electrons transferred per molecule, atom or ion.

Significance of Faraday :
It is found experimentally that 1 coulomb of electricity deposits 0.001 119 gm of silver. The amount of electricity needed to deposit 108 gm or 1 gm equivalent (or 1 log = 96500 coutombs. This is the value of 1 gm atomic wei&%%of silver = 0.001 119 Farad ay . Thus Faraday is the quantity of electricity needed to deposit or liberate one gram-equivalent weight or one gram atomic wt. or 6.023 x lo2, number of atoms (Avogado number). To deposit one gram-equivalent weight, 1 Faraday is needed.

Example 14.1 A current of 0.5 amp., when passed through a solution of a chloride of formula ACl,, for 3520 seconds, gave at the cathode 1.28 g of a metal. (a) If the atomic mass of A is 197.0 g mol-', find n (b) If the cell is c o ~ e c t e d in series with another electrolysis cell in which water is electrolysed. what will he volume at S.T.P. of oxygen collected at the anode? Solution:
(a) No. of faradays passed = 4 = OS5 3520 = 0.01824 F 96500 A grams of A ,96500 C required , For depositing n 197 gram or one Faraday = n

Therefore , the formula of the chloride is ACl,

Equlllb~~&~~tr~heml~ r g The evolution of b)

oxygen at the anode of another cell can be represented as

1 mol of 02 = 22.4 lit (at S.T.P.) = 4F 22 - 4 lit x 0.01824 F = 0.102 litres. vol. of 0, = 4F Faraday's laws are exact and are applicable to aqueous solutions as well as fused salts. If there are several processes taking place at an electrode, Faraday's laws are applicable to all the electrode processes taken together. With reference to each electrode reaction, it is usual to associate the term current efffcfency, to indicate how much of the total current is made use of in a process. It is defined as the ratio of the actual amount of the material deposited at or dissolved from an electrode and that expected theoretically on the basis of Faraday's laws. Example 14.2 By the passage of 0.06 faradays of electricity 1.057 g of nickel (atomic mass. 58.71) was deposited at the cathode. If hydrogen is also evolved simultaneously what is the volume at S.T.P. of hydrogen evolved at the cathode? What are the current efficiencies for Ni deposition and hydrogen evolution? Equivalentweight of Ni = 2 5871 Solution :

58.7 grams of Ni. The current 0.06F electricity should deposit 0.06 x 2
x 100= 60.0 8.The rest of the efficiency for Ni deposition = 1-057 0.06 x 58.71 current utilised for hydrogen evolution is equal to 0.06 - 0.036 = 0.024F. The volume of hydrogen evolved at S.T.P. can be calculated from the fact that 2F of electricity is required to evolve 22.4 of H2 at S.T.P. 22.4 x 0.024 F = 0.2688 1or 268.8 ml at Therefore ,volume of hydrogen liberated = 2F S.T.P.

SAQ 1
What volume of oxygen would be liberated from an aqueous solution of NaOH by a curreht of 2 amperes flowing for 1 ; hrs at 2 7 C and 1 am pressure.

SAQ 2
1. An aqueous solution of sodium sulphate containing sulphuric acid is elecuolysed between Pt electrodes. What will be the products obtained at each electrode ? calculate the amount of products liberated or dissolved at each electrode if a current of 2.68 amp is passed for one hour through an aqueous solution of CuSO, (atomic weight of Cu = 63.54)

2.

Aqueous solutims of electrolytes, like metallic conductors, obey Ohm's law (Eqn. 14.4) which enables us to calculate the resistance (R) from the EMF (E) and current (i) E=iR (14.4) The passage of direct current (d.c.) through the solution causes electrolysis and consequently there will be a decrease in the concentration. The resistances of aqueous solutions of electrolytes are always measured using an alternating current (a.c). The resistance of any elecuical conductor is proportional to its length (I), and inversely proportional to its area of cross section (A), R a - I or A

In Eqn. 14.5, the constant of proportionality, p, is called the specific resistance or resistivity of the conductor. It is the resistance offered to the passage of electric current by a conductor of length 1.0 cm having a cross sectional area of 1 cm2. From ~ q n14.5, . it is seen that the units of p are ohm cm (C G S) or ohm m (S I). The resistivity, being the resistance between opposite faces of a one cm3 of material, is very useful in comparing the resistances of different conductors. In electrolytic conduction, it is the conductance (G) which is reciprocally related to the resistance, that is more useful. For the comparision of conductances, the spec#ic conductance or conductivity (K) which is the reciprocal of resistivity is useful. The conductivity is given by Eqn. 14.6
.

The units of K are ohm- c m or o h m m- The reciprocal ohm is some times called mho and sometimes the siemens (S). This quantity G is thus the conductance between the opposite faces of a one cm3of the material. Conductivities of a few substances are given in Table 14.1 Table 14.1 :Conductivities of a few substances at 298 K Substance Silver copper Aluminium 1.0 M KC1 (aq) 0.01 M KC1 (aq) 0.1 M acetic acid (aq) water G/ohm cm6.38 x 1 6

' '

' '.

'

5.80 x 1 6
3.80 x 1 6

1.10~ lo-' 1.41 x l u 3 5.20~ 1r4 4.0 x 10-*

In table 14.1, the conductivities are listed in the decreasing order. It will be seen that in the case of aqueous solutions of electrolytes, conductivity depends on concentration. For the sake of comparison of conductivities we need to use the

Equilibria & Electrochemistry

solutions of electrolytes of the same concentration. One molar solutions of sodium ~ each + ion transports chloride and magnesium sulphate may be used. In ~ g sG', two units of charge whereas in Na+ Cl- each ion transports only one unit of charge. However, if the concentration is expressed in equivalents per litre (normality), one equivalent of any electrolyte gives rise to positive ions with a total charge of IF and negative ions with a total charge of 1F. The conductance of a volume of a solution containing 1 equivalent of an electrolyte confined between two large parallel electrodes 1 cm apart is called the equivalent conductance A Let 1 gram equivalent of an electrolyte be dissolved in V cm3 of the solution. Since the electrodes are 1 cm apart, the solution will cover the electrode surfaces upto an area of V cm2. From Eqn. 14.6.

Under these conditions the conductance G is the equivalent conductance, A. Substituting for A = V c d ,I = 1 cm, we have Eqn. 14.8. Here KV is numerically equal to the equivalent conductance. A=KV (14.8) In Eqn. 14.8, V is the volume of the solution in cm3 containing 1 gram equivalent of the electrolyte. If the concentration of the aqueous solution is c equiv. lit-': 1.gram equivalent of the electrolyte will be present in l/c lit or 1000/c cm3. Thus V is 1000 cm3/c. Substituting in Eqn 14.8, we get a more useful form of this equation.

The units of (A) will thus be 1000cm3lit-' ohm" cm-' or ohm- cm2equiv- The equiv. litlast term is usually dropped since it is implied in expressing A as the equivalent conductance. The molar conductivity A,, is defined by Eqn. 14.10

'

'

'.

Where M is the concentration in mol dm3and cmis the concentration in mol m-3. It will be seen that for electrolytes like magnesium sulphate.

It is convenient to use equivalent conductance, since it is a measure of the current-carrying ability of all the ions from 1 gram equivalent of any electrolyte.

14.5 MEASUREMENT OF CONDUCTANCE OF AOUEOUS SOLUTIONS OF ELECTROLYTES

The specific and equivalent conductances of aqueous solutions of electrolytes are calculated by determining the resistance of the electrolytic conductor contained in a conductance cell of known dimensions I and A. As indicated earlier, an alternating current (a.c) is to be used to prevent elec~olysis. Usually an a.c of 1000 to 2000 cycles per second is used so that the small amount of electrolysis taking place in one half of the cycle is reversed in the opposite half of the cycle. Platinum electrodes, on which platinum black is deposited. are used so that the electrode reactions occur rapidly and there is no accumulation of the products of electrolysis. A Wheatstone bridge arrangerncnt is normally used to measure the resistance of the solution (Figurel4.2). The point of contact P is moved along the wire AB till no current is detected in D. The resistance is so adjusted that the balance point is almost midway between A and B. Since a.c. of this frequency is audible, an earphone detector is used. A minimum nohe in the earphone indicates the balance point under these conditions. In place of an earphone, analog or digital detectors can also be used.

Resistance

Figure 142 :Muwement d & t m a o f m aqueous dutim o f an ele~lolyle using 8 Whewume bridge unmganau.

Resistanceof the cell - AP (14.1 1) Known resistance ( R ) PB The resistance of the cell can be calculated using Eqn. 14.1 1. Once the resistance of the cell is known, the value of K and A are calculated by using Equations 14.6 and 14.9 respectively. Calculation of K requires a knowledge of the dimensions 1and A of the cell. The direct measurement of 1 and A is rather difficult,once the cell is assembled. For a given cell, both 1and A are constants and the ratio 1/A, called the cell constant (k), can be calculated by measuring the resistance of a solution of 0.1N KCI, whose specific conductance is accuratelly known. The conductance cell is now standardised and can be used to calculate conductivity of any solution containing an electrolyte. 14.6 can be' written in terms of the cell constant as Eqn. 14.12

Since ordinary distilled water has an appreciable conductance, specially prepared water called conductivity water, with a resistance of nearly lo6ohms, is used to prepare all the solutions. Since the resistance varies with temperature, the cell must be kept in a constant temperature bath. Conductance or specific conductance is an additive property. In an aqueous solution containing several electrolytes, the total conductance is given by Eqn. 14.13.

In Eqn. 14.13, , , G is the conductance of water used in preparing the solutions and the summation applies to all the electrolytes present. In the case of strongly , , G is so small that it can be neglected in compais~n with conducting solutions, the conductance of the electrolyte solution. For weakly conducting solutions,

For maximum sensitivity in measuring high conductances (low resistances) a cell with a high value of k is used. A cell with small electrodes separated by a large distance is used (Figure 14.3a). Conversely, for the measurement of low conductances (high resistances), 1/A should be as small as possible by having large electrodes separated by a short distance (Figure 14.3b). Example 14.3 A conductance cell, when filled with 0.1 molar solution of KCI, has a resistance of 33.2 ohms. The same cell after washing, rinsing etc., has a resistance of 300 ohms when filled with 0.1 molar solution of acetic acid (HOAc), and 55.2 ohms when filled with 0.03 molar solution of sodium sulphate. The specific conductance of 0.1M KC1 at this temperature is 0.01 164 ohm- cm' The conductivity of water used to prepare these blutions is

' '.

Equilibria & Eleetrochemlstry

Fig. 1 4 . 3 :&e

o f conductance cell f o r the mcasumnent o f (a) low resistana (high conductance) (b) high resistance (lowconductance)

7.6~ 1r40hm-' cm-' at this temperature. Calculate (a) the cell constant, and (b) equivalent and molar conductances of the solutions of (i) acetic acid and (ii) sodium sulphate. Solution:

Therefore, In order to calculate A, the specific conductances are required. (i) A ,

(b)

K , , = 1000C

This includes h e contribution from h e water used for preparing the solution. Therefore, K due to HOAc alone = 1.287 x 10-~-7.6 x 1 r 4= 5 . 2 7 ~ lo4= 5.27 x 10-4ohm" cm-' Therefore,

In case of acetic acid, equivalent weight = molecular weight, and hiOAc = AHOAc = 5.27 o h m cm2

'

Therefore,
K ~ sSO, , -6 . 9 9 2 ~1r3-7.6 x 1r4=6.233x 1 r 3o h m 1cm-I

1 moleofNa$304= 2molofNa+= 1 molof

s@-=~F

Equivalent weight of Na2S04= molecular weight / 2 or 0.03 M solution of Na2S04= 0.06 N Na2S04 Therefore ,

= 2 X 103.8 or 207.6 ohm- l c d

14.6

RESULTS OF CONDUCTANCE MEASUREMENTS AND THEIR INTERPRETATION

Electrolytic Condudlon

The specific and equivalent conductances of all electrolytes are found to vary with concentration. As the solution is diluted. the specific conductance increases and reaches a limiting value in the case of many electrolytes. This limiting value is called the equivalent conductance at zero concentration (A0) or at infinite dilution (A?, since the value of A0 does not increase further with dilution. The results are represented as plots of A against 6 , where c is the concentration in equivalents per litre (Figure 14.4). From Figure 14.4, it is seen that in the case of solutions of strong acids, bases and their salts, the plots are'reasonably linear and the values of A do not vary appreciably with dilution. Tfiese are called strong electrolytes and in these cases it is possible to obtain thevalues of A0 by extrapolation. the case of weak electrolytes like acetic acid, ammonium hydroxide etc., A increases rapidly as the solution is diluted, especially at low concentrations. In these cases, value of A0 cannot

In

Figure 14.4 :The variation of equivalent conductance of a few elecirolyles with ancmration (Figure not to rcale)

Arrhenius attempted to explain the variation in K and A with concentration using his electrolytic dissociation theory. According to this theory, an electrolyte dissociates . into ions when dissolved in water and the degree of dissociation (a ) increases with dilution. The conductance of a solution of a given electrolyte depends on the number ions, and also on their velocities. Arrhenius assumed that dilution does not affect the velocities, but increases the number of ions available from an electrolyte. At infinite dilution, a tends to be unity and at all other concentrations, a < 1. When the solution containing the electrolyte is diluted, though the extent or degree of dissociation (a) increases, the number of ions per cm3 of the solution decreases. The specific conductance is the conductance between the opposite faces of a one cm3 of material and since 1 cm3 of material contains a lesser number of ions than before, K decreases with dilution. The increase in (A ) with dilution was attiibuted to an increase in the number of ions available from one equivalent of an electrolyte at high dilutions. At infinite dilution, since a = 1, the value of (A ) does not vary and becomes equal to A', which is the limiting value of A. Since a = 1 corresponds to A', Arrhenius proposed A that the ratio -should be a measure of a, at any concentration. Thus, A0

The values of a experimentally determined from colligative properties of aqueous solutions of electrolytes agreed quite satisfactorily with those obtained from the conductance measurements. Ostwald verified Arrhenius theory by applying the law of mass action to the equilibrium existing between an electrolyte and its constituent ions. Consider a solution of normal acetic acid (a weak electrolyte) in equilibrium with H+and OAc' ions. If a is the degree of dissociation, the equilibrium

&-kanis(~

concentrations of H+ OAc- ,and HOAc are ac,c a and c ( 1 - a ) respectively. If V is the volume of the solution containing one equivalent of an electrolyte. V = l/c. The expression for the equilibrium constant (K), given by Eqn. 14.15

is known as the Ostwald's dilution law. The value of K was found to be reasonably constant only for weak electrolytes and not for strong electrolytes. Strong electrolytes have been shown to consist of ions even in the solid state and = 1) at all in aqueous solutions the electrolytes are completely ionised (a concentrations. According to the Debye-Htikel theory, which is applicable to both strong and weak electrolytes, as a result of the interionic attraction the velocitiek of the ions are influenced. Each ion is surrounded by an ion cloud of oppositely charged ions (ion atmosphere). This ion cloud retards the movement of the central ion. In the case of strong. completely dissociated electrolytes, the variation in conductivity with concentration can be traced to this retardation which increases with concentration. At very high concentrations, ions associate into ion pairs, and so, the effective number of conducting species will be less than in the absence of ion association. As the solution is diluted, the ions are father apart, and the density of the ion cloud decreases. The interionic forces of attraction will be less, the speed of the ion increases, and so the equivalent conductance increases. At infinite dilution, the ions are so far apart that there are no interionic forces of attraction. Thus, the equivalent conductance reaches a maximum value. For weak, incompletely dissociated electrolytes, changes in conductivity occur as a result of an increase in the degree of dissociation with increasing dilution.

14.7 KOHLRAUSH'S LAW AND ITS USEFULNESS

At infinite dilution, in the absence of any interionic forces of attraction, each ion of an electrolyte can be expected to behave independently. Kohlrausch found that the , (NaX) was the same irrespective of the nature of the anion, difference. A , ( KX ) - A - A0 (KY), where X and Y X. Similarly, a constant value for the difference A0 (KX) are anions, was observed. These results could be explained if it is assumed that A,, for each salt is considered to be the sum of the equivalent conductances of the constituent ions (ion conductances) at infinite dilution. He put forward his law of independent conductance of ions as, "at infinite dilution, each ion makes a definite contribution to the equivalent conductance of an electrolyte, whatever be the nature of the other ion of the electrolyte". This can be expressed as Eqn. 14.16 A0= A!+ k : (14.16)

: and 5 : are the ion conductances at infinite dilution of the cation In this equation, k and the anion respectively. TI4e ion conductances of a few ions are given in Table 14.2
From this table, it will be seen that for polyvalent ions, the values are only for one equivalent and not for a mole. The conductances reflect the amount of current that these ions can carry. Thus, one should compare the conductances
)10 ( Na+) )10

( f ~2 ) .)10 ( f Fe3 ) etc.. since in each case. we are referring t o

+
+

the amount of species associated with 1 mole of electrons. Also. A' but A : 1 (5 MgSO, ) = 53.1 + 80 = 133.1 ohm- ' cm2 equiv7 ' ( MgSO, ) = 106.2 + 160= 266.2 ohm- ' cm2mol- '

Table 14.2 :Ionic equivalent conductances a t infinite dilution of a few ions a t 298 K* Cations

Electrdytk Condudlon

1 :
349.8 77.8 77.3 73.4 73.5

Anions OW
( 1/4 ) Fe( CN : ) ( 1/3) ~ eC (N ) ~ ( 1/3 ) P O : ( 1/2)

7 1 :
If

H+ .
Rb+ Cs+ NH: K+

197.6 111.0 99.1 92.8 83.0

0 : -

NO;

Formate Acetate It was seen earlier (Figure 14.3) that values of A, for strong electrolytes can be obtained by extrapolation. In order to obtain A0 values in the case of weak electrolytes like acetic acid. we can use A0 values of suitable strong electrolytes as, _ shown below:

=kO(H')+ ~'(oAc-) In the case of sparingly soluble salts. the saturated solution is so dilute that further dilution does not change the value of A. Hence it is assumed that A = A'. Thus,
'1 1 AO(f B ~ s ~ ~ ) = A ~ ( ~ B ~ c ~ ~ ) + A ~ ( ~ N ~ s ~ ~ ) - A ~ ( N ~ c ~ )

Example 14.4

1 1 At 298K. the A0 values of NH4CI ;- BaC12 and - Ba ( OH ), in o h m cm2 are 2 2 149.9, 139.9 and 262.2 respectively. Calculate A0 of NH40H.
I

'

Equlllbrla & Electrochemistry

Solution:

= 149.9 + 262.2 - 139.9 = 272.2 ohm1cm2

Example 14.5

4 1 The h0values of - BaCl - N$S04 and NaCl in o h m c d are 139.9, 130.1 2'2 2 1 and 126.5 respectively. Calculate the he0 of y BaSO,.
Solution:

= 143.5 ohm1 c d

Example 14.6 When water with a specific conductance of 1.1 x o h m cm- is saturated with BaSO,( s ), the saturated solution is found to have a specific conductance o h m cm- I. Calculate the solubility in n~ole/lit of BaSO, in of 4.6 x water at 298 K. Solution:

concn. of BaSO, in equiv/lit = 1 mol of BaSO, = 2 equiv.

ld x 3.5 x 1 r 6 = 2.44
143.5

Therefore, concn. of BaSO, in mol/lit = 1.22 x lo-'

SAQ 3
1.
A decinormal(0.1 normal) solution of sodium acetate, when placed between two electrodes each of area 1.5cm2, and placed at a distance of 0.72 cm, has a resistance of 524 ohm. Calculate the specific and equivalent conductances of this solution.

2.

The equivalent conductances (A0) on ohm' cm2 at infinite dilution of NaCl, HCOONa and HCl are 126.4, 109.6 and 426.1 respectively. Calculate (Ao) (HCOOH). The equivalent conductance of 0.01 N H ' ] . HCOOH is 50.7. Calculate the degree of dissociation and [

14.8 CONDUCTOMETRIC TITRATIONS

The conductance of a solution is the summation of the contributions from all the ions present. It depends on the number of ions per unit volume (concentration), and also on the ion conductances. During the course of a titration, the concenuations of the ions change, and so conductance also changes. In this method, the variation of the conductance of the solution during the course of a titration is followed. It is not necessary to determine the actual specific conductance of the solution, and any quantity proportional to it can be used. For a given cell with a known cell constant, K is inversely proportional to resistance R, and so one can use the reciprocal of resistance or conductance to follow the titration. The conductance changes with dilution, and so it is usual to add a concentrated solution of the titrant from a burette. Since this procedure involves the measurement of resistance, one can use this method in the case of coloured solutions, colloidal solutions and even dilute solutions. The use of conductance to locate h e end points in titrations is based on the changes in the slope of the plot of conductance versus volume of titrant (titration curves). This change of slope may be due to the presence of ions of high conductance in the solution, or weakly ionised or insoluble compounds after the equivalence point. Thus, it is possible to follow the progress of neutralization and precipitation titrations.

Electrolytic Conduction

Acid-Base Titrations
The conductometric titration curve for the neutralisation of a strong acid ( H ' C1-) by a strong base (Na' OH-) is given in Figure 14.5(a). The reaction can be represented as:

H+ + C1-

Na+ + OH-

--+

Na+ + Cl- + H, 0

+--+
Species present in the conductance cell initially

+--+
Titrant

The highly conducting hydrogen ions initially present in the solution are replaced by the sodium ions having a much smaller ionic conductance. Hence, the conductance of the solution decreases as the base is added (the descending position of the curve in the figure). Beyond the equivalance point, further addition of a strong base inuoduces highly conducting OH- ions in solution. Since these are not used up in the reaction, the conductance increases in direct proportion to the excess of base added ( the ascending portion of the curve). Normally, the conductance of the solution is determined after successive additions of the alkali, such that points covering the range before and after the end point are obtained. Two straight lines are drawn through these points. The point of intersection of the two straight lines gives the volume of the alkali required to neutralise the given volume of the acid. If a weak base like an aqueous solution of ammonia (NH40H) is used as a titrant in determining the concentration of the strong acid, the descending portion of the curve is similar, since this represents the decrease in conductance as a result of replacing the hydrogen ions by the ammonium ions. After the equivalence point, the conductance will remain almost constant because of the low conductance of NH40H compared to NH,CI [Figure 14.5(b)]. The neutralisation titrations of weak acids or bases are rather difficult. A weak acid like acetic acid (HOAc) is present mostly as unionised molecules and the solution has a low conductance due to the small amounts of H+ and OAc- ions. The neutralisation reaction can be represented as

+-+
Species present in the conductance cell initially

HOAc

Na'0I-It-+ -+Na++OAC+K,O

Titrant

As neutralisation proceeds, the common ion formed, i.e.. the acetate ion, supresses thc ionisation of the acetic acid (Sec 14.11). Hence, initial addition of small amounts of an alkali result in a decrease in conductance. With further addition of sodium

Volume o f T i t r a n t

F ~ U14.5 R : Carductmetric T~uaticm curves (a) HCI against NaOH

(b) HCI against N H 3

hydroxide. the cohductance of Na+ and OAc- ions exceeds that of acetic acid and conductance of the solution increases. After the equivalence point, thcre is a sharp increases in conductance due to the Na+ and OH- which are no more required for neutralising HOAc [Figure 14.6(a)]. If NH,OH is used as a titrant, the initial portion of the curve is similar to that in Fig 14.6(a). After the equivalence point, there is practically no change in conductance because of the very small conductance of NH,OH [Fig.14.6(b)l.

Volune o f T i t r a n t
Figure 14.6 :Conductanetrictitration curves

(a) Acetic acid against NaOII (b) Acetic add against NH3

Precipitation tiuations are based on the fact that the contribution of the ions of the sparingly soluble salt to the conductance of the solution is rather small. The reaction between K+ Cl- and Ag+NO; can bc represented as
te-9

Species present in the conductancecell initially

+ +

->

AgCl(s)+K++NOj

Tiuant

The net result being the replacement of C1- by NO; of almost equal conductance, there is practically no change in conductance as the titration is performed. However,

beyond the equivdlence point the addition of Ag' NO; increases the number of ions in solution and so the conductance increases [ Figure 14.7 ]

ElectrolyticCoadudlon

Volume o f Titrant

Figun 14.7 :Condudmetric urntion KCl against A D @ (tilrant)

14.9 ACIDS AND BASES

- -

Acids and bases were originally defined by Arrhenius as substances capable of giving rise to hydrogen ions and hydroxide ions, respectively, in solution. This definition applies only to aqueous solutions. In order to account for the acid-base behaviour in solvents like liquid ammonia, liquid sulphur dioxide, glacial acetic acid etc., Lowry and Bronsted, independently put forward the proton transfer theory. According to this theory, an acid is defined as a substance with a tendency to loose a proton and a base is a substance with a tendency to gain a proton. This definition applies to all solvent systems. For an acid to donate its proton, some proton acceptor (a base) must be present. Similary a potential base will accept a proton only in the presence of a proton donor. When an acid loses a proton, the remaining portion of the molecule will have a tendency to accept a proton and hence it is a base. In general one can write

The acid and the base which differ by a proton are said to be conjugate to one another. When a potential acid like hydrogen chloride gas is dissolved in water, the solvent functions as a base to accept the proton to form the hydronium ion, H30+. This means that the hydrogen ion in aqueous solution is not the bare proton, H+, but a ) The simplest formula, H30+,is solvated proton of the general formula H+(H20 , obcained when n is unity. This reaction can be represented as HCl + H,O t -$ H30t +C1(1) Acid- 1 Base-2 Acid-2 Base-1 It will be seen that C1- is the conjugate base of HCl and H30+is the conjugate acid of the base, H20. The dissolution of a weak acid like acetic acid (HOAc) in water to give a i acid solution can be represented as HOAc + $0 3 H30++ OAc(2) The acidity of an aqueons solution of an acid is attributed to the presence of H,O+. Greater the concentration of this hydronium ion, stronger is the acid. Since HCl is a stronger acid compared to acetic acid, the position of equilibrium for reaction (1) is almost to the right, and in the reaction (2), it is almost to the left of the equation. Alternatively, one can consider that the tendency of C1- to accept a proton is far less compared t that of OAc'. Thus, acetate ion is a stronger conjugate base than CT.In general, the conjugate base of a strong acid is weak and vice versa. If a solute like ammonia gas is dissolved in water, the solvent water acts as an acid and the reaction 1 % can be represented as

Equilibria & Electrochemistry

Solvents Eke water which can either take up protons or donate protons are said to be amphiprotic. Solvents like liquid HF, liquid HOAc which can give protons are called H , ,pyridine etc., which act as bases are protogenic solvents. Solvents like liquid N said to be protophilic. Solvents like benzene, toluene etc. which cannot donate or accept protons, are called aprotic solvents. Strong electrolytes are completely ionised in aqueons solutions and the concentrations of the ionic species in solution can be calculated from the concentration of electrolyte. For example, in a 0.05 M solution of barium chloride, [Ba2'] = 0.05 M and [Cl- ] = 0.1 M. In the case of weak electrolytes, whatever is dissolved may not be in the form of ions. Only a small fraction of the solute gives rise to ionic species in solution. In such cases, the concentrations of the ionic species can be calculated from the application of law of mass action to such equilibria. Equilibria involving electrolytes like acids, bases and sparingly soluble salts in aqueous solution, are included in ionic equilibria.

14.10 ACID-BASE EOUILIBRIA

The ionisation equilibria in the case of weak acids (HA) and bases (B) can be represented as HA + H20 and B+H20 2 BH'+OH (4) respectively. The equilibrium constants for these equilibria are given by equations 14.17 and 14.18 respectively.

2 H30' + A-

(3)

The weight of one litre of water at 298 K is 997 g and this corresponds to 55.4 mol of water in a litre. In its reaction with solutes, the change in the concentration of water is rather small and hence one can consider [ H20 ] to be a constant in these equations. Consequently, these can be written as Equations 14.19 and 14.20 respectively.

In Eqn 14.19, H30' is represented as I? for the sake of simplicity. The equilibrium constant K, is called the dissociation or the ionisation constant of the acid and Kb is that for the base. The molar concentrations of the various species can be calculated from the degree of dissociation and concentration (Sec. 14.6). If a is the degree of dissociation of the acid HA of concentration c,, the concentrations of the various species in equilibrium are [H']=[A-]=c,a Similarly, if write and [ H A ] = c , ( l - a ) .

P is the degree of dissociation of the base B of concentration cb, we can

It is assumed that [ H+] or [ BH' ] are available only from the dissolved solutes. If there are other sources for these ions, the concentrations from these sources must also be included (Sec.14.11).

It will also be seen that K, and K,, in terms of the degree of dissociation, are given by Equations 14.20 and 14.21 respectively.

ElechPlgtk Condudlam

Since a and p can be measured conductometrically~Sec.14.6), it is possible to evaluate K, and K,. If the ionisation constant is known, it is possible to calculate he degree of dissociation and also the various concentrations (Example 14.8).

Example 14.7
A 0.1 M solution of NH3 has an equivalent conductance of 3.60 o h m cm2 at 298 K. At the same temperature. the ion conductances in ohm'. c d of N e and O H ions are 73.4 and 197.6 respectively. Calculate (1) the degree of dissociation, (2) the concentration of O H ions, and (3) the dissociation constant, Kb.

'

'

Solution:

= 1.788 x lo-'

Since,

( l - $ ) ~ l , ~ , ~( iP .e. ~) 1 c. 7 6 8 ~ 1 0 - '

The latter value is within 1.2%error of that in (3).

Example 14.8
The ionisation constant of formic acid is 2.0 x at 298 K. Calculate of a 0.01M solution of fonnic acid at the degree of dissociation and [ H+] 298 K. Solution: From Eqn. 14.20,

on simplification we get a quadratic equation in a,i.e., a2+ 0.02 a - 0.02 = 0 Solving this equation we get,

Therefore, The ionisation constant is a measure of the strength of an acid or a base. Thus, nionochloroacetic acid (K, = 1.4 x 10- 3, is stronger than formic acid (K,= 2.0 x 1 r 4 ) , which is itself stronger than benzoic acid (K,= 6.3 x lo-'). Similarly, among the amines, the base-strength decreases as diethyamine > ethylarnine > ammonia > aniline

(Kb= 1 . 0 0 ~

(Kb=4.66x

(Kb= 1.77 x lo-')

(Kb=3.8x 1F14 '

Equllibtia & k % c h d m i s t r y

SAQ 4
1. Fill in the blanks : Conjugate Acid Conjugate Base

~ ~ o ; y ~

2.

HCOOH A decimolar solution of acetic acid is 1.33% ionised. Calculate the [H'] and the ionisation constant ( K , ) . At the degree of dissociation (a). same temperature, enough solid sodium acetate is dissolved in one litre of 0.1 M acetic acids so as to make the concentration of the salt equal to I .O M. What will be the [H+]of the resulting solution ? (Hint a << 1)

14.11 COMMON ION EFFECT

Equilibria involving weak electrolytes are affected by the presence of salts having the same cation or anion as those derived from the electrolyte. The LeChatelier's principle (sec. 12.6) predicts that the degree of dissociation of the weak electrolyte should decrease in the presence of a common ion. This is referred to as the common ion effect and is very useful in controlling the concentration of ions derived from the weak electrolyte. For example, one can make use of this effect to decrease the [ O m available from an aqueous solution of NH, by adding enough ammonium chloride, so that only the hydroxides of iron aluminium and chromium are precipitated (Sec.14.16). It is possible to calculate the concentrations of the various ionic species, if the equilibrium constant for the dissociation of the electrolyte is known. For example,

'

With the addition of sodium acetate, the value of [CH3C007 is increased and in must order to maintain the constant value of K, at a given temperature, [H30+] decrease and [CH3COOH]must increase. Hence the ionization of CH3COOH(a weak electrolyte) is suppressed. Example 14.9 At 298K, the [H+]of a 0.01M solution of an organic monobasic acid (HA) is 1.732 x M (a) calculate the ionisation constant of the acid at this temperature. (b) To a litre of this solution of the acid enough of solid NaA is added, so that the concentration of NaA is 0.02M. What will be the value of [Ht] after the addition of NaA? Assume that there is no volume change as a result of the dissolution.

~olution: (a) H A 2 ~(1-a) Since,

Therefore.

H+

+
ac

Aac

a c = [ H+ 1 = 1.732 x 1 r 3 , c being 0.01 M ,a = 0.1732

(b)

The addition of the common ion A- is expected to decrease the degree of dissociation. I f a' is the degree of dissociation, the dissociation equilibrium can be represented as ,HA c ( 1 -a')

2 H++A(a'c) ( a ' c + x )

Where x is the concentration of the added common ion

Since, ( a' )' c << a' x

the equation can be written as

solving, a' = 0.0178

' c = 0.0178 x 0.01 and so, [ H+] = a

= 1.78 x
The common ion effect is also relevant in the dissociation of weak polybasic or plyprotic acids. These are acids capable of donating more than one hydronium ion. For example, %C204, H2C03are weak dibasic acids, whereas H,PQ ,H3As04are weak tribasic acids. In aqueous solutions, these acids lose protons' in a stepwise fashion and each step is characterised by a dissociation constant. Thus, in the case of H3P04, the dissociation equilibria can be represented as

H W - .H~ ++PO~; K,= 1.2%1 r 1 2 The values of the dissociation constants for successive stages of a polyprotic acid always decrease steadily, as shown in the case of phosphoric acid. This is because of the difficulty with which a proton must be lost from ionic species like H2POi and H * - in the second and third stages, respectively. Compared to the loss of a proton from a neutral molecule, these processes are much more difficult. The [ H+ ] is given by [ H+1= [ H+ 1from step 1 + [ H+] from step 2 + [ H+ ] from step 3. However, the [ H+] from steps 2 and 3 are very small as a result of the common ion effect due to the [ W ] from the first step. It therefore the [ H+] is equal to that from the first step. It will be noticed that species like H2PO; and H @-can function both as an acid and a base. Such species are said to amphiprotic.

14.12 ACIDITY AND ALKALINITY OF AQUOIUS SOLUTIONS

Since the solvent water is capable of losing as well as gaining a porton, there must be a proton transfer equilibrium as shown below:

The very small electrical conductivity of pure water indicates the presence of ions in low concentrations. This indicates that the dissociation of water to give H+and O H ions must be taking place to a small extent. Applying the law of m a s s action to the self-ionisation of water, we have

Since most of the water remains undissociated, [ H20 1 may be considered to be constant, and so, Eqn.(14.22) simplifies to Eqn.14.23

The equilibrium constant K, being the product of ionic concetrations, is called the ionic product of water and has a value of 1.0 x 1W l4 at 298 K. In any aqueous solution, equation 14.23 should hold good. Since pure water is neither acidic nor basic but neutral, [ H+ ] = [ O H ] = 1.0 x 1 r 7 . This condition of,equality is also a condition for neutrality in aqueous solutions. If [ H+] is greater than 1.0 x M, the solution is acidic and if it is less than 1 r 7 , the solution is alkaline.
A convenient scale of acidity and alkalinity. which avoids the use of negative exponents in expressing [ H+ 1, was introduced by Sorenson. He defined the pH of a solution as the negative logrithrn of the hydrogen ion concentration (Eqn. 14.24)

In this scale, a pH equal to 7 represents the condition of neutrality. For an acidic

solution of [ H+ ] = 1.0 x 1 r 4,pH = 4 and for an alkaline solution in which [ O H ] = l . O x 10-~or[H+]=-- Kw - 1.0 x l r 9 , the pH will be 9. This method IO HI has the advantage that all states of acidity and alkalinity upto one molar solution can be expressed by a series of numbers from 0 to 14. Thus it will be seen that, for acidic solutions, pH < 7, and for alkaline solutions. pH will be > 7 .This kind of p(X) notation can be applied to express the concentrations of other ions, ionisation constants and other equilibrium constants. Thus from Eqn 14.23 -log[H+]-log[OH]=14or pH+pOH=14 (14.25) Equation 14.25 enables one calculate pOH from pH and vice versa. The same reciprocal relationship that one finds between [ H+ ] and pH holds in all these cases. ; pK, = 3.70) is a stronger acid than benzoic Thus, formic acid ( K, = 2.0 x ; pK, = 4.21 ) .Similarly, among bases, ammonia acid ( K, = 6.3 x ( K, = 1.77 x 1 r 5 ;pK, = 4.75 ) is stronger than anline ( K, = 3.8 x 10; pK, = 9.42). The pH of solution can be measured using a pH meter (Sec.13.10). Though the pH scale covers a range of 6 to 14, in very strongly acidic solutions the pH may be negative and in very strongly alkaline solutions it may be greater than 14.

Example 14.10 Calculate the pH of the following solutions (1) 1.0 M HClO, (2) a solution in which [ H+] = 3.564 x 1 r 4and (3) a solution in which [ O K ] = 2.0 x 1W3M.

Solution:

Electr~blle Condudion

pOH = - log[ O H ] = ( -5.301 ) = 2.691 pH= 14- 2.69= 11.31 Example 14.11 (3) Calculate the [ H+] in the following (1) a solution of pH = 4.75, and (2) pH = 12.31 Solution: (1) log[H+]=-pH=-4.75= 5.25 Therefore, (2) log [ H+ I = - 12.31= i3.69 Therefore,
[ H+]= 4 . 8 9 ~

M ; [OH-] = 1 . 0 lo-" ~ =O.O~M 4.89 x 10- l3

SAQ 5
1. a) An analysis of water in a lake indicated that [W] = 3.2 x 1 r 5mol/lit. What is the pH of the water in the lake ? Is it acidic or basic ? b) Calculate the [ H ' ] that corresponds to each of the following values of pH. i) lemon juice pH = 2.25 ii) pH of milk of magnesia = 10.50 The ionic product of water is 1.0 x 1W14

2. a) Given that K , of acetic acid is 1.8 x 1w5,calculate the pH of 0.15 M solution of sodium acetate.
b) If the dissociation constant of ammonium hydroxide is 1.8 x 1v5. What will be the pH of 0.15 M solution of NH4N03?

Equllibrln & ElortroehmWr~

14.13 BUFFER SOLUTIONS

A careful control of pH is important in life processes, in industry and in certain analysis. For this purpose, suitable buffer solutions are used. When reasonable amounts of an acid or an alkali are added to an aqueous solution of ammonium acetate or a mixture of ammonium chloride and ammonium hydroxide, there is practically no change in the pH of the solution. The resistance that a solution exhibits to changes in pH upon the addition of acid or alkali is called buffer action and solutions exhibiting this property are called buffer solutions. Buffer soultions usually consist of (1) a weak acid (acetic acid) and its conjugate base (acetate ion), or (ii) a weak base (ammonia) and its conjugate acid (ammonium ion), or (iii) a weak base (ammonia) and a weak acid (acetic acid). Buffer solutions are used mainly for resisting changes in pH or for providing solutions of known pH. The buffer action will be explained using two examples. Consider the buffer solution consisting of HOAc and NaOAc. If H+ions are added, these are removed by OAc- to form the unionised acid.

I f O H ions are added, these are removed by the reaction with the unionised HOAc to give OAc- ions.
HOAC+ OH-

-+

H20 + OAC-

The pH of the solution thus remains practically constant. In the case of a buffer solution consisting of NH3 ( NH40H ) and NH4C1the following reactions

account for the buffer action. In a similar fashion, if a buffer solution of ammonium acetate is used, the buffer action can be explained as follows H++ OAC- (from buffer) -+ HOAc NH3 + H20

H : (from buffer) -+ O H +N

The pH of a buffer solution can be calculated by considering the effect of adding a common ion (Sec.14.11) to the weak acid or the weak base equilibria. Consider a buffer solution consisting of a weak acid (HA) and its salt like NaA. This is a special case of the ionisation of the acid in the presence of a common anion, A-. The dissociation constant K, of the acid is given by Eqn 14.19

If the initial concentration of the acid is c, and that of the salt NaA is c, and a is the degree of dissociation in the presence of NaA, the equilibrium concentrations of the various species can be expressed as follows. [H+]=c,a, [A-]=(c,a+c,)and [HA]=c,(l - a ) Substituting these values in Eqn 14.19, we have

As explained in Example 14.9, a < < 1 and so c, ( 1 - a ) G c,. Considering the [ A- 1, it will be realised that it is only the added salt NaA, that is the major source of A- in solution, since [ A- ] available from HA will be very small as a result of the common ion effect. So c, a <<c, or ( c, a + c, ) c,. Thus Eq. 14.26 can be written as

K . = [*I

[ Salt ] [Acid]

ElectrolyUcConduction

The above equation can be rearranged to give Eq. 14.27

[~ t . 1

=K,W
[ Salt ]

Taking logarithms and changing the sign throughout, we have Acid -log[~]=-log~.-l og~or [ Salt ] pH = pK, Salt ] + log [[Acid ]

Equation 14.28, known as the Henderson equation, is useful in calculating the pH of buffer mixtures and also the amounts of the buffer components required to prepare the buffer solution. A similar equation for the system B - BIF) ( NH,, - N@ ) is obtained from the expression for the ionisation constant of the base .(Eq.14.20)

As in the case of A : i - A- system, invoking the approximations, [ BH' ] 5 [ Salt 1, and [ B I e [ Base 1. we have K~=[OHI (Sllrlor [ Base ]

=K,W [ Salt 1

Taking logarithms and changing the sign throughout equation 14.29, we get

Buffer solutions show buffer action only if limited quantities of H+or O H ions are added. The buffer capacity of a mixture may be regarded as the amount of acid or alkali that a buffer solution can use up without suffering a change in pH. It is found [Salt] or [Salt] is that buffer solutions have their greatest capacity when the ratio [acid] [base] equal to unity and that the concentrations used are about 1.OM. For satisfactory buffer action or if the pH is to remain constant within f 1 ,these ratios must lie between 10 and 0.1: Thus, the useful ranges of buffer solutions lie between pH = pK, f 1 or pOH = p Kb I 1. For example, p K, of acetic acid is 4.75 and the useful range of the acetic acid-sodium acetate buffer is 3.75 to 5.75. Similarly, for NH, - NH4 C1 buffer mixture, the useful range is 8.25 to 10.25. Example 14.12 A solution is prepared by dissolving 0.20 mole of sodium formate and 0.25 mole of formic acid in water and making the total volume upto 250 ml exactly. The ionisation constant of formic acid is 2.0 x Calculate (i) the pH of this solution, (ii) the change in pH by adding 1.0 ml of concentrated HCl (normality = 10.0) to 250 ml of this solution, and (iii) the change in the pH by adding 1.0 ml of 10 N NaOH solution to another 250 ml portion of the buffer solution. Solution:
i,

pH = pK,

+ log

[ Salt ] [ Acid 1

The pK, of formic acid = -log ( 2 x 1V ) = 3.70 [Salt1 =

Om2 'O0O = 0.8 moll lit 250

Equilibria & J3kIroehemLFtry

Similarly, [Acid] = Oe2'

250

lMX) = 1.0 molPit

Therefore, pH = 3.70+ log @ ! = 3.60 1.o (ii)

lx no. of moles of HCl added = 1.0 m

= 0.01 mol

lit x 10 mol lit1000ml

'

[HCl] added = 0.04 momit ( Since, .O1 mol is contained in 250 ml) The added HCI reacts with the conjugate base HCOO- as HCOO- + H+ ---4 HCOOH Hence the concetration of HCOOH resulting from this reaction is equal to the concentration of HCl added. Thus [HCOOH] = 1.0 + 0.04 + 1.04 mol/lit. This reaction between HCOO- and H+ also decreases the concentration of the salt. sodium formate by 0.04 momit. [Salt] = 0.8-0.04 = 0.76 molllit Therefore, pH after the addition of HCl = 3.70 + log-076,- 3.56 1.04 Therefore, Change in pH is only by 3.56-3.60 or -0.04 units. The pH decreases by 0.04 units. no.of moles of NaOH = 0.01
[ O H ] added = 0.04 momit

(iii)

The added O H reacts with HCOOH as shown below. O K + HCOOH 0.04 momit %O

+ HCOO-.

Thus the [HCOW increases by

Therefore, [ HCOO- ] = [Salt] = 0.8 + 0.04 = 0.84 molPit Simultaneously [HCOOH] decreases by 0.04 molpit [HCOOH] =1.0 - 0.04 = 0.96 momit
0.84 pH after adding the alkali = 3.70 + log - 3.64 0.96

Therefore. change in pH = 3.64 - 3.60 = 0.04 The pH of the solution increases by 0.04 units Now, let us define hydrolysis and consider different types of salts formed by combinations of acids and bases. The details of hydrolytic equilibria will be considered in the next section.

Hydrolysis of Salts
Definition : The hydrolysis of a salt is defined as the interaction of the ions of a salt with either the H+or the O W ions of water to form a basic or an acidic solution.

If the ions of the salt interact with O W of water, the salt is said to be hydrolysed. The resulting solution is acidic. If the ions of the salt, dissolved in water react with H+ ion of water, the salt is said to be hydrolysed. The resulting solution is basic. Here, we sunmarise the formulae used and derive them in the next section.

Types of salts
Based on this definition of hydrolysis, thc salts arc classified as follows into four types : (i) Salts of strong acids and strong bases eg. NaCl NaCl is the salt of a strong acid HCI and the strong base NaOH.

NaCl

2 Na++Cl-

(ii) Salts of weak acids and strong bases : eg. CH3COONa sodium acetate is formed by the combinalion of CH3COOH, a weak acid and NaOH, a strong base. H20

-+

H++ OH-

or wcakly ionised acetic The acetate ions interact with the H+ ions to Torn1 uniot~iscd acid. These salts are hydrolysed and ihc rcsul ling sol 111ion is basic. (iii) Salts of strong acids and weak bases : eg. NH4Cl Ammonium chloride is formed by thc inrcrnc~ion of thc strong acid HCI and weak base, NH,OH. H20

--+ H++ OH-

NH;

+ OH- ---+ NH,OH

The ammonium ion interacts with the hydroxyl ion to form ammonium hydroxide, the salt is hydrolysed andathe resulting solution is acidic. (iv) Salts of weak acids and weak basis eg. CH,COONH, Ammonium acetate is formed by rhc in~craclion ol' ammonium hydroxide, a weak base and acetic acid.

NH:

+ OH- ---+ NH40H

Acetate ions interact with. H+ ions lo for111 aci~ic acid and hydroxyl ions and Ilydroxidc. TIlc salt is hydrolysed and ammonium ions interact to form ammonii~n~ !he resulting solution is neutral.

14.14 HYDROLYTIC EOUILIBRIA

Salts are formed by the neutralization of an acid by an cquivalcnt amount of a base or vice versa. However, aqueous solutions of salts likc sodium acetate, sodium cyanide, ammonium chloride, etc., are not neutral and ~ h pll c is nor cqual to 7.0 in these cases.

Electrochemistry

Only in the case of salts formcd from strong acids and bases, the aqueous solutions are neutral. An aqueous solution of sodium acetate has a pH greater than 7.0 (alkaline). whereas that of ammonium chloride has a pH less than 7.0 (acidic). In the case of sodium acetate, thc acctate ion present in solution is a strong base and abstracts protons from water as shown below OAc-+ H20

2 HOAc + O H

The hydroxide ions formed in the reaction are responsible for the solution having a pH > 7.0. In the case of ammonium chloride, the N q being the conjugate acid of a weak base, is capable of donating a proton to water to give rise to H30+ions.

The formation of H,O+ explains to acidic nature of the solution. This interaction of h e abstraction of a proton from the solvent, or the ions of the electrolyte leading to L h c solvcnt is called hydrolysis. It will be noticed that only donation of a proton to L strong conjugate acids and bases get hydrolysed in aqueous solution. Weak conjugate bases like Cl- ,NO; do not undcrgo hydrolysis. This interaction leads t o a decrease in the concentration of a conjugatc bases like cG- ,s2,C2 @- etc., which are normally uscd to prccipitatc cations. Hcnce ways and means of preventing hydrolysis are important. The extcnt to which thc hydrolysis rcaclion proceeds is determined by the equilibrium constant, called the hydrolysis constant (K, ) of the salt undergoing hydrolysis. From Kh it is possible to calculate the pH of such aqueous solutions. Consider the salt of a wcak acid (HA) and a strong basc (MOH), for example NaOAc. The anion, Aundergocs hydrolysis as

The reaction can be considcred as hydrolysis of the salt MA or dissociation of the conjugate base, A-. For this equilibrium, the hydrolysis constant (Kh ) can be written as Eqn. 14.29 in which [ H20 ] is considered as a constant.

K , = [HA] [ O H ]
[A-I The above'cquation can bc written as [ H A ][ H I ] [ o K ~ --Kw (14.30) [H+l[A-l K a From the hydrolysis equilibrium, it is sccn that [ HA ] = [ OH-] and if Kh is rather small, the extcnt of hydrolysis will also be small. Thus the equilibrium concentration of A- can bc taken to bc equal to 111coriginal concentration of A ' i.e., Equation 14.29 can bc writtcn as Eqn. 14.31
Kh-

Since, [ H+] [ OH- ] = K,, Eqn. 14.31 becomes

From equations 14.30 and 14.32, we get

Taking logarilhms and multiplying by -1 throughout, we get

1 1 1 pH=-pK,+-pK,+-1og.c 2 2 2

Similarly, for the salt (BHX) of a weak base (B) and a strong acid (HX) like NH,Cl. the hydrolysis reaction can be written as

Electrolytic Condudlon

, ,can be writlen as follows. The hydrolysis constant K

Since [ B ] = [ H30+] and [ BH+ ] s c ,one can wrilc

From Equations 14.35 and 14.36 we get

For the salt (BHA) of a weak acid (HA) and a weak basc(B), thc hydrolysis reaction is

The hydrolysis constant is

Considering the dissociation equilibirum of HA

since [A-] = c, Eqn (14.40) can be written as

Substituting for [HA] in Eq. 14.39, we get Eq. 14.40

If a is the degree of hydrolysis, Eq. 14.29 and 14.35 can be written interms of a as eqn. 14.42.

Here K represents K , or K , , as the case may be. If Eqn. 14.43.

a << I,Eqn. 14.42 simplifies to

From Eq. 14.43 ,it will bc seen that extent of hydrolysis increases as (i) K , increases, i.e., as the temprature increases, (ii) as K decreases, i-e.. the weaker the acid or the base, and (iii) as c decreases i.e., as the solution gets diluted. Thus it is seen that at a given temperature, the degree of hydrolysis (a)can be decreased if a high concentration of the salt is used. For a salt of the type BHA, if is the degree of hydrolysis, we can write the equilibrium as

~(1-PI From Eqn. 14.38

~(1-PI

cP

cP

, will be large since K , . Kb a product of two small quantities, is it will be seen that K rather small. This means that hydrolysis will take place extensively and is independent of concentration. At higher tempratures, the extent of hydrosis will be quite considerable.
Practically, all the cations except those of alkali and alkaline earth metals undergo hydrolysis in aqueous solution to give acidic solutions as shown in the case of salts of ~ 1 ,
+

and so on. As in the case of other equilibria, it will be seen that the hydrolysis reaction can be supprcsscd by adding one of the products of the equilibrium. In this case, the hydrolysis reaction can be suppressed by adding acids. Thus, while preparing aqueous solutions of salts of polyvalent cations, it is advisable to add acids to prevent hydrolysis. Example 14.13 Calculate (i) the hydrolysis constant ( K , ) (ii) the degree of hydrolysis (a) and (iii) the pH of a 0.1M solution NH,CI. The ionisation constant of NH3 ,K , ,, at this temperature is 1.80 x 10-5. What will be the degree of hydrolysis if 1.OM solution of NH,CI is used? The ionic product of water is 1.0 x 10- l4 at this temperature. Solution: The hydrolysis reaction is

N H :
From Eqn. 14.35,

+ H,O 2 NH, + H30+

K , = a2 a2c ( Because, a h rather small) (1-a)

Elecbolytic Conduction

iii) From Eqn. 14.37,

14.15 PRECIPITATION EOUILIBRIA

In chemical analysis, precipitation is an important process. In qualitative analysis, the
separation and identification of the cations and anions is bascd on precipitation reaction. In quantitative analysis, one should make sure whcthcr the desired constituent is quantitively precipitated or not. An understanding of thc solubility product, which is based on the application of thc law of mass action, is t h e f o r e quite essential. When a saturated solution of an electrolytc is in contact with thc solid solute, there exist an equilibrium between the ions in the solution and the solid. Consider such an equilibrium between MA and its ions M+ and A-.

Applying the law of mass action to this hctcrogcncous systcm in cquilibriurn. we can write the expression for the equilibrium constant, K.

In a saturated solution, [MA(s)] can be considerd to be a constant, since it is not likely to change as a result of the dissolution proccss. Hcncc Eqn.14-44 can be writte'n as Eqn 14.45 Ksp=[M+1 LA-] (14.45) Whatever has dissolved is assumed to bc cxisting as ions. The ionic product represented by Eqn. 14.45 is called the solubility product and applies to any saturated solution. However, it is of practical inlcrcst only in lhc case of sparingly soluble salts. The solubility product expression (Eqn. 14.45) being an equilibrium constant, depends on the stoichiometric coefficients of thc ionic spccics, is., the formula of the spearingly soluble electrolyte. For a 1.1 (AgC1) or 2.2 (BaSO, ) or $3 ( Fe PO, ) electrolytes of the formula MA, the expression for K , , can bc writtcn as follows. Let S be the solubility in water in mol/dm3 or molllit of thc salt, at a given temperature. Since whatever is dissolved

exists as ions, the ionic concentration arc [Mn+]=[An-]=S Therefore, K,=[M"+] [A"-]=s' It is assumed that MA(s) is the only source lor thc ions Mn+and An-. . (14.46)

For a 1.2 (Ag2Cr04) or 2.1 (CaF, ) electrolyte, the equilibria can be expressed as M2A and MA,

2 2 W + A%
3 ~ ' + + A2
(14.47) (14.48)

respectively. The solubility product constants for h$ A and M 4 are given by equations 14.47 and 14.48 respectively

K , = [ M + ] ~[A2-]

K,=

[M"] [ A-1'

If S is the solubility in moVdm of the salt M2A, then [ M+] = 2s and [ A'- ] = S. Substituting these values in equation 14.47 we get Eqn. 14.49 as the expression for the solubility product of M , A

K~~=[M']'[A~-]=(~S)~(S)=~S~

(14.49)

Similarly for M A,, if X is the solubility in movdm3 , [ M2 + ] = X and [ A- ] = 2 X.The expression for the solubility product of MA, is given by Eqn.14.50 [M2+] [A-]~=(x)(~x)~=~x~ Example 14.14 Write down the solubility product in terms of the solubility (S movdm3 ) of the elecirolyle Sb, S3 Solution: Sb,S3(s) (14.50)

2 2sb3++3s22s 3s
s2-13

K,,=[Sb

3+ 2

or(2~)'(3S)~

= 108 s5

14.16 APPLICATION OF THE SOLUBILITY PRODUCT

14.16.1 Solubility and Ksp
The solubility product is a measure of the solubility of the salt in water at a given temperature. From equations 14.46, 14.49, 14.50 and Examplel4.14, it will be realised that for the sake of comparision one should consider b e IZ,values of salts of similar formulae. Thus Agl (K,, = 1.0 x 10- 16)is less soluble than AgCl ( KT= 1.1 x 10-lo). Also, Ca F2( K , , = 3.2 x 10- l1 ) is less soluble than Mg F2 ( K , = 7.0 x 10- ). Howcvcr, instead of K,,, one can also compare the molar solubilities (S) of salts. Thus Ag2CrQ ( K, = 1.7 x 10' l2 and S = 7.5 x 10'' M ) is more soluble than Ag CI ( KT= 1.1 x 10-''and S = 1.05 x 10"M ).

14.16.2 The Effect of added electrolytes on the equilibrium between the sparingly soluble electrolyte and its constituent ions.
The added electrolyte, irrespective of its nature, influences this equilibrium. When the added eleclrolyte has an ion in common with the salt MA, we have b e common ion effect (sec 14.11). which is relevant to the precipitation equilibria. The constant K,, defines the maximum concentration of the ions in solution bat can remain in equilibrium wiih ihe sparingly soluble salt. Consider the effect of adding H+C1-to Ag C 1(s).

AgCl ( s ) Ag++ ClAs indicated earlier, the [ Cl- ] in equilibrium with AgCl(s), in the absence of any other source.of Cl- ,is approximately 10-5 M. If [ Cl- ] exceeds this value, [ Ag' 1 also should decrease. (Le Chatalier principle). In other words, the solubility of the sparingly soluble salt will decrease in the presence of a common ion, or the added Ct combines with Ag+ to form AgCl(s). Thus, we can say that precipitation will occur if the product of the concentrations of the ions (ionic product) exceeds the solubility product. This is the condition for precipitation to occur. It will also be seen'that if the concentrations of one or both the constituents are decreased either by formation of a complex or a weakly ionised substance, th solubility product equilibrium is disturbed. Hence more of the salt dissolveshQis is the basis for the dissolution of AgCl in NH,. Here Ag' forms a complex [ Ag ( NH, )2 ]+and if the [ NH, 1 is quite high, practionally all the Ag' is converted into to the complex. Hence, more of AgCl dissolves in order to restore the equilibrium condition. Ultimately, all the solid can be dissolved in NH,. This can be represented as AgCl (s )

2 Ag++ Cl-

14.16.3 Applications in Qualitative Analysis

Among the sulphides. those of Hg, Cu, Pb, Cd, Bi. As, Sb and Sn are less soluble than those of Co, Ni, Mn, and Zn. Hydrogen sulphide is used as a source of sulphide ions to precepitate these sulphides. Being a weak electrolyte, its overall dissociation can be represented as
,
k
)

H2S

2 2H++s2-

constant For a given concentration of dissolved H2 S. we can write [ s2-1 = [ H+ I .Thus, we decrease [s2-] by increasing [ H+] so that only the less soluble sulphides of group II get precipitated. Once these are removed, the other cations can be precipitated by increasing [ s 2 - ] available from H,S by making the medium very weakly acidic or alkaline. Thus h e group IV sulpliides are precipitated by passing H2S into an arnmoniacal medium containing the cations of his group. Similarly. by decreasing [ O K ] available from a weak electrolyte like aqueous NH3 ( NH40H ) by adding NH4CI, it is possible to precipitate the less soluble hydroxides of Fe. Al and Cr in group 111. Under these conditions. the hydroxides of Mg. Ni, Mn, Co and Zn are not precipitated.

Example 14.15 The specific conductance of conductivity water, at 298 K, is 1.61 x 10d ohm1cm-'. When saturated with pure AgCl(s). its conductivity m '' .The ionic equivalent conductances at increases to 3.41 x l ~ ~ o h mc infinite dilution of Ag+and Cl- in ohm- cm2 are 61.9 and 76.3 respectively. Calculate (i) the solubility of AgCl(s) in moll lit. (ii) the solubility product of AgCl(s) and (iii) the solubility of AgCl in 0.001 N NaCl solution. Solution:

'

As indicated earlier (Sec 14.7), A G A' in this case. h0(~g~1)=61.9+76.3 138.2ohm-' = cm2

Where S is the solubility of AgCl(s) in cquiv / lit or moll lit.

lr6= 1.302~ l(r%ovlit Thercforc, S = lWOx 138.2

ii)

Ksp = [ Ag' ] [ Cl- ] = s2(Eqn. 14.46)

=( 1 . 3 0 2 ~ lo-')'

iii)

In the prcsencc of 0.001 NaCl, the [ Cl- ] available from NaCl is 0.001 and this is >> [ Cl- ] available from AgCl, in the absence of a common ion. One would expect the [ Cl-] available from AgCl(s) to be decreased by h e c o m n ion effect-(Sec 14.4.31). Lets' be the mhbi of AgCl(s) in the prescnce of added C t . One would expect S ' << S. Ag Cl ( s )

Ag'

Cl(S+O.001)

s'(s'+0.001)= 1 . 7 0 ~ 10-lo S' is rather small and so S' x S' will be <<0.001 S' Therefore, 0.001 S' = 1.70 x 1 moll lit

s'=1 . 7 0 ~ l w 7 mol/lit
The value of S in thc absence of C1- is 1.302 x 10" momit Example 14.16 To a solution containing 0.01 mol of Fe3' and 0.01 mol of ~ g " and ' 2 mol of NH, C1 in a litrc of the solution, enough ammonia is added with stirring till the for Fe ( OH ) and Mg ( OH )2 concentration of NH, is 2.OM. The values of KP are 3.8 x and 3.4 x 10- respectively. Which cation gets precipitated? The dissociation constant for thc rcaction,

NH,

+ H,O 2 N@ + O H

is 1.8 x lo-5 at this Lcmpcraturc. Assume that there is no volume change. Solution: In order to find out which cation gets precipitated we have to determine the ionic products for cacll hydroxide and find out which product is greater than the solubility product. Fe(OH), F ~ ~ ' + ~ o; H K,= [Fe3'] [ 0 H 1 3

2
+

The conccnlrations of' [ FC, ] and [ ~8 '] are 0.01M each. In order to find [ O H ] we have lo considcr thc dissociation equilibrium of NH,, that is the source of O H

1 in solution = [ NH:
= 2.0 M

] from added NH, C1+ [

N K ] derived from.added NH3.

= [N H : ] from NH, Cl (since the other quantity is very small)

NH:l 1 . 8 lvs= ~

[OH] -2 . 0 ~[ O H ] [ NH, I 2.0

:. Thcrcforc, [ O H ] = 1.X x lo-'

The ionic products arc
(i) [~e~[ 'o ] H]~=o.o( ~1 . 8 1 ~0 . ' ) ~ = 5 . 8 3 2 ~ 1 0 - "

(ii) [~~~+][0~]Z=0.01(1.8~10~~)'=3.24~1~'~ The ionic product in the case of Fe ( OH ) viz.,

5.832 x 10- I' is >> K, ( 3 . 8 x 1r3* ) and so it is Fe ( OH )3 that gets precipitated.

In the case of Mg ( OH ),. the ionic product ( 3.24 x 10- l2 ) is less than its K , ( 3.4 x 1 0 I '). and so. it is not precipitated.

SAQ 6
1. The solubility of Mg F2 at room tempcraturc is 0.0012 moll lit Calculate the solubility product of Mg F,. What will be the solubility of Mg F2 in 0 . 1 M MgSO, ?

2 .

The solubility product of lcad chloridc ( PbC12) is 1.6 x 1r5. If 500 ml of 0 . 0 3 M NaCl is mixed with 500 ml of 0.3 M lcad nitrate. will there be a precipitation of PWI, ?

14.17 SUMMARY
Eleclrolytes, either in the molten state or in aqueous solution. conduct electricity and undergo chemical reactions at the elcctrodcs. This process is callcd electrolysis. Faraday's laws of electrolysis summarise thc quantitative rclationship between the quantity of electricity (ampere-seconds or coulombs) passcd and the extent of chemical reaction that takes place. One Faraday, equal to 96500 C, is L h e quantity of electricity required to deposit or dissolve onc cquivalcnt of a substance.
I f instead of a direct current. an altcmating currcnl is uscd. it is possible to measure the resistance (conductance) of electroryrrz conductors. In the casc of aqueous solutions of electrolytes, the conduclivily dcpcnds on conccnlration. For a comparison of conductivities. equivalcnt conductanccs arc q u itc useful. The variation of aqucous solution of of specific and equivalent conductances with diluiio~l electrolytes could be accounted for by lllc Arrhenius thcory of electrolytic dissociation. The Debye-Huckel theory of intcriot~ic artraclion provides a more reasonable explanation of this bchaviour. Kohlrausch's law of independent ion-conductances at infinite dilution cnablcs oric lo calculate thc cquivalent conductance at iflinite dilution of wcak clcctrolytcs and sparingly soluble electrolytes. The change in the conduclancc wilh concentralion forms the basis for carrying out acid-base and precipitation titrations conductometrically.

An important application of conductomclry is thc calculalion of the degree of dissociation of weak acids and bascs. By applying Ihc law of mass action to equilibria involving weak acids and weak bascs, onc can calculalc rhcir ionisation constants. Similarly, one can calculate the solubilities and solubiliry products of sparingly

Equlllbrlr & Ekdroehaaldq

soluble salts. The term "common-ion effect" refers to the influence of electrolytes, having the same cation or anion as those derived from the weak acids, weak bases or sparingly soluble electrolytes, on equilibria involving such species.' Systems involving weak acids (bases) in the presence of common ions show buffer action. They are useful in resisting the changes idpH of such a buffer system. The pH can be calculated using the Henderson equation. The conjugate b$es of weak acids are strong enough to abstract a proton from water which results intan alkaline solution. Similarly, the conjugate acid of a weak base is a strong acid, capable of donating protons to water. The interaction of the ions of a salt with either the Ht or the OW ions of water is called hydrolysis. The solubility product principle, common ion effect and hydrolysis find extensive applicatio& in chemical analysis.

14.18 GLOSSARY
Electrolysis
: Chemical decomposition caused by the passage of elcctricity.

Faraday : The charge contained in one mole of electrons. Electrolytic conduction : The movement of ions of an electrolyte under the influence of an applied EMF. Conductivity water : Watcr obtained by repeated distillations, where conductivity is only due to the conductivities of H+and OH- ions. Oswalds dilution law a2c : K =where K = equilibrium constant, a = degree (1 -a)' of dissociation and c, the concentration of ttle electrolyte. : The theory wherein the molecules of acids, bases and salts arc dissociated into constituent ions.
:
A, = A",

Arrhenius theory Kohlrausch's law

+ Loa. where. the terms refer to the equivalent

Conductometric titrations Acids & bases

conductances of the solution. cations and anions respectively at infinite dilution. ~itratibns wherein the conductance of the electrolyte : solution is measured as a function of the volume of the titrant added.
: An acid is a substance capable of accepting electrons,

while a base is a molecule capable of donating electrons.

:

- log [ H ' ] . The Henderson equation pH = pKa +'

is useful for calculating the pH. [Acid] Solutions of a weak acid and its salt or a weak base and its salt whish resist changes in pH when acids or bases are added to them. Thc interaction of the ions formed from a salt with or OH-ions of water to yield basic or acidic solutions.
log

Buffer solutions

Hydrolysis Solubility product

In MA $ Mt

+ A-,

KSp =

[m] [A7

14.19 ANSWERS TO SAQs

SAQ 1
40H- ---+
02

+ 2H20

1 1hrs. = 5400 scc. 2

4 x 96500 Coulombs liberate = 32 g of 0,

2 x 5400 Coulombs liberate = 32 x 5400x 2 96500, g

nRT Volume of O , V =-

SAQ 2
1) 2)

H, at cathode and 0 , at anode 3.177 Cu is deposited at cathode and 3.177 g of Cu is dissolved from anode

SAQ 3
1) 2)

SAQ 4
1)

Conjugate base :s@- and HCOOConjugate base :NH; and Hz PO,

2)

a=0.0133; [ ~ + ] = 1 . 3 3 x 1 0 - ~ ; ~ = 1 . 7 7 x 1 O[-~ ~+ ;]=1.?7xlO-~ a) pH = 4.49. Water in the lakc is acidic b)i)5.6x1w3 ii)3.2~10"'

SAQ 5
1. 2.

a) 8.97 b) 5.03

SAQ 6
1) -2)

Y e s ,Since ion product [ pb2 1 [ C1- ] = ( 0.15 ) ( 0.015 ) is ' greater than Kip.
+

'

FURTHER READINGS
1.
2.

James E Brady and John R Holum, Fundamentals of Chemistry, John Wiley and Sons. (1981 and later editions) Leonard W Fine and Herbert Beall, Chemistry for Engineers and Scientists, Saunders College Publishing (1990) J.C Kuriacose and J. Rajaram. Chemistry in Engineering and Technology Volumes 1 and 2, Tata McGraw-Hill Publishing Company Ltd., (New Dclhi (1988) Atkins, P.W., Physical Chemistry, ELBS and the Oxford University Press. 5th Edition (1993) Caslcllan Gilbert, W.; Physical Chemistry, Addison-Wesley, Reading (Mass). 5th Edition. Cottrell A. H., Introduction to Metallurgy, Edward Arnold, London. Daincls Farrington and Robert A. Alberty. Physical Chemistry, John Wilcy, Ncw York. Ferguson F.D. and Jones T.K. Phase Rule. Butterworths, London. Findlay Alcxandcr; Phase Rule and its Applications, Dover Publications, New York. Glastonc Samual and David Lewis; Elements of Physical Chemistry; Macmillan, London. Kuriacose J.C. and Rajararn J.; Chemistry in Engineering and Tcchnology, Vol. 1, General and Physical Chemistry; Tata McGraw Hill Publishing Co. Ltd., New Delhi. Mahan Bruce. H., Univcrsity Chemistry. Narosa Publishing House, New Dclhi (1985). Maron Samucl H. and Jerome B. Lando; Fundamentals of Physical Clicmistry, Macn~ilan, Ncw York. Moore Wallcr, J., Physical Chemistry, Orient Longmans, London.

3.

4.
5.

6 .
7.

8.
9. 10. 11.

12. 13. 14.