ACID-BASE THEORIES

Arrhenius Concept.
After the advent of Arrhenius theory of electrolytic dissociation an acid was regarded as a compound which in aq. solution produces hydrogen ions (H+) and a base was regarded as a compound which in aq. Solution produces hydroxyl ions (OH-).So the properties of acidic and basic solutions are due to the H+ ions and OH- ions produced from the acid and the base respectively.

Eg. CH3COOH + H2O H+ + CH3COO-

Ca(OH)2 + H2O Ca2+ + 2OH-

Acids have some common properties. They have a sour taste, they react with carbonates & bicarbonates liberating CO2,they turn blue litmus red, they liberate H2 by reaction with metals like Mg, Zn etc. Basic solutions contain excess of OHions. It turns red litmus into blue. A solution of a base has a soapy touch.

Limitations.
1 Arrhenius definition applies only to aq. Solution. In solvents such as liquid ammonia etc acidbase behaviour has been observed. Eg. NH4Cl behaves as an acid and NaNH2 behaves as a base in liquid NH3. 2. This theory regards only compounds containing OH groups as bases. However it is well known fact that substances such as pyridine, piperidine,etc. behave as bases in aq. Solutions even though they do not contain hydroxyl ion.

Proton Transfer Theory.

Concept Of Bronsted & Lowry:Acid H+ + Base Acid: Proton donor Base: Proton acceptor. Eg. CH3COOH + H2O H3O+ + CH3COONH3 + H2O NH4+ + OHHCl + H2O H3O+ + ClLimitations: Applicable only to reactions involving proton transfer.

Acid base which differ by a proton is called as conjugate pair. In conjugate pair if one of the species is strong the other will be weak. A weak acid has a strong conjugate base and a strong acid has a weak conjugate base. Acid A a proton = conjugate base of the acid A. Base B + a proton = conjugate base of the base B.

Substances like water and HCO3- which can behave both as an acid and as a base are called amphoteric substances or ampholytes. HCO3- + H2O H2CO3 + OHHCO3- + NH3 NH4+ + CO32-

Lewis Concept Of Acids and bases.

An acid is a species which can accept a pair of electrons and a base is a species which can donate a pair of electrons. Consider the molecules of NH3,H2O etc. These molecules have lone pairs of electrons as indicated by their structures. These can donate the lone pair of electrons to a proton H+ to form coordinate bonds.

+
H-N-H H and H-O-H H A species which contains incomplete octet of electrons is a Lewis acid.
+

F
B- F molecule has only 6 electrons in the valency F

level,NH3 molecule having a lone pair of electrons can donate the lone pair to the BF3 to form H3NBF3.

Ionic Product Of Water:Water has very low electrical conductivity. It ionises very slightly, and can act both as acid & as a base. H2O H+ + OHH + + H2O H3O+ + OHk = [H+][OH-] [H2O]

Ionic product of water kw =[H+][OH-] [H2O]may be taken as constant kw = 10-14 a constant at a given temperature 298K. In a neutral solution [H+] = [OH-] =10-7 In acidic solution [H+]>[OH-] (< 10-7moldm-3) In an alkaline solution [H+]< [OH-] (>107moldm-3)

pH Scale:A special method of expressing the acidic or basic nature was proposed by Sorensen. He suggested the pH scale which expresses the conc. Of hydrogen ions in the solution. pH = - log10[H+].Higher the value of pH,lower is the acidic nature. The conc.of hydroxyl ions can also be expressed in terms of pOH.

pOH = - log10[OH-].Higher the value of pOH lower will be the conc. Of [OH-] ions in the solution. In water or neutral solution, [H+] = [OH-] = 10-7M pH = pOH = 7 pH + pOH = 14 If pH < 7, solution is acidic. If pH = 7,solution is neutral. If pH > 7,solution is alkaline.

Buffer Solutions.
For many purposes in chemistry, industry and biology, it is necessary to have solutions whose pH does not change much even on the addition of appreciable amounts of strong acids or strong alkalies. Such solutions are called buffer solutions. A buffer solution is one which can resist change in its pH value on the addition of an acid or a base.

The pH of an aq. Solution of ammonium acetate is 7. But the addition of 1ml of N HCl solution or 1ml of N NaOH solution to a litre of ammonium acetate solution will not cause any appreciable change in its pH. Thus ammonium acetate soution is a buffer as it can resist alterations in its pH value on the addition of an acid or a base. The capacity of a solution to resist alteration in its pH, is known as its buffer capacity.

Types of Buffer Solutions: Buffer Mixture Of Weak Acid And Its Salt:Prepared by mixing equimolar solutions of acetic acid and sodium acetate .The mixture thus contains CH3COOH molecules as well as CH3COO- and Na+ ions. Let us consider the buffer action of this mixture,

Suppose a strong acid is added to the above mixture, H+ + CH3COO- to form feebly dissociated CH3COOH.Thus the H+ ions added are neutralised by the acetate ions present in the mixture. If on the other hand, a strong base is added,the OH- ions added are neutralised by acetic acid present in the mixture: OH- + CH3COOH CH3COO- + H2O. Again, there is very little change in the pH value of the solution. It should be clear from the above mechanism of buffer action that reserve acidity of CH3COOH- CH3COONa buffer is due the presence of CH3COOH and reserve alkalinity is due to the presence of CH3COO- ions.

Buffer Mixture Of a Weak Base and Its Salt:A mixture containing equimolar solutions of ammonium hydroxide and its largely dissociated salt,NH4Cl,constitutes another good buffer.The mixture contains undissociated NH4OH as well as NH4+ and Cl- ions. If a strong acid is added, H+ + NH4OH H2O +NH4+ If a strong base is added, the OH- ions added are neutralised by NH4+ ions forming very slightly dissociated NH4OH. In this case reserve acidity is due to the presence of NH4+ ions and reserve alkalinity is due to the presence of NH4OH.

Calculation Of pH Values Of Buffer Mixtures.

Buffer mixture of a weak acid and its salt. Consider a buffer solution containing a weak acid HA and its highly ionised salt NaA. [H+] = Ka[acid] [salt] -log[H+] = - logKa + log[salt]/[acid] pH = pKa + log[salt]/[acid](Hendersons eq.) Enables to calculate pH values of buffer solutions made by mixing known concentrations of a weak acid and its salt.

Buffer mixture of a weak base and its salt. If a buffer solution consists of a mixture of a weak base and its salt,it can be easily shown that [OH-] = Kb [Base]/[salt] pOH = pKb + log [salt]/[base]. Knowing pOH, the pH value can be easily calculated from the relation pH+ pOH = 14

Importance Of Buffer Solutions.

Buffer solutions are of great importance in medicines and in biological systems. Most of the biological fluids have definite values of pH & their pH values are maintained within proper limits by buffer action. For eg. the pH of blood is maintained 7.35 due to buffer action of sodium carbonate+ sodium bicarbonate buffer present in blood. All the functions of blood can take place when the pH is around this value. Any marked change from this value shows pathological conditions such as coma.

Titration-acidmetry-alkalimetry.
Titrimetric Analysis (Volumetric):A quantitative method of analysis dealing with the volumes of solution and their measurements is termed Volumetric Analysis. In this method, a known volume of one solution is taken in a conical flask. To this is added other solution of a substance, little at a time from the burette till the reaction is complete. This process is known as titration. The stage during titration at which the reaction is just complete is known as the equivalence or end point. End point is detected by the addition of suitable substance called indicators that changes its colour when the reaction is complete.

Standard Solution is one in which exact amount of a substance present in a definite volume of solution is known. Strength Of Solution: The amount of a substance present in a definite volume of solution is termed strength of the solution. It is usually expressed as the amount of the substance in one litre of the solution. Following are the various units used for expressing strength of solution. Normality(N), Molarity(M),Molality(m).

Normality Equation.
According to the law of equivalence , substance react in the ratios of their equivalent weights. It means that if the solution of a substance 1 is titrated against the solution of a substance 2 then at the endpoint we can write as follows: N1V1 = N2V2 where N1 and N2 are the normalities of two solutions 1and 2 and V1 and V2 are the volumes of two solutions 1 and 2 respectively.

From this equation,the unknown normality of a solution can be calculated. Let this be x now,N1V1 = N2V2. If N1 and V1 and V2 are known, N2 = x can be calculated by the derived equation. N2 = N1V1/ V2. Calculation Of strength of solution: Strength = Normality X equivalent weight Percentage purity of the substance = w/x X100

Various substances used for making standard solutions in volumetric analysis are classified into the following two types. (i) Primary Standard: The substance whose standard solution is prepared by dissolving directly its known amount in a definite volume of solvent or solution is known as a primary standard. Eg. Anhydrous Na2CO3,Oxalic acid,K2Cr2O7 etc. (ii) Secondary Standard: Those substances whose standard solutions cannot be prepared directly by weighing its definite amount and then dissolving it in a definite volume of water is called a secondary standard. The solution of this type of substance firstly prepared is of approximate strength which is then standardised with a standard solution of a primary standard. Eg. Alkali hydroxides,KMnO4 etc.

The reactions used in volumetric analysis belong to various types .Accordingly the volumetric determinations can be divided into the following methods:i) Acid base titrations. ii) Oxidation-Reduction titrations. iii) Precipitation titrations. iv) Complexometric titrations.

Acid-Base Indicators.
Acid-base indicator is a substance which changes its colour within limits with variation in pH value of the solution to which it is added. This gives an easy method of determining pH value of a solution by simply adding a suitable indicator and noting the colour. The pH range over which the colour change occurs, varies considerably from one indicator to another.

Some useful indicators:-

Indicator

pH range

Methyl orange Methyl red

3.1 4.5 4.2 6.3

Colour in acidic solution. Red Red Colourless Yellow

Colour in alkaline solution. Yellow Yellow Pink Red

Phenolphth- 8.0 9.8 alein Cresol red 7.0 8.1

The Theory Of Acid-Base Indicators.

According to Ostwalds Theory, a hydrogen ion indicator is either a weak organic acid or a base. The unionised molecule has one colour and the ion furnished by it,on dissociation, has another colour. Let the indicator be an acid of formula HIn.Then,its ionisation in solution may be represented as HIn H+ + In-

The unionised molecule HIn has one colour,say,colour A, while the ion In- has another colour,say,colour B. The equation for the above equilibrium may be written as Kin = [H+][In-] / [HIn] where Kin is known as indicator constant. Since the species In- and HIn have different colours, the actual colour shown by the indicator will depend on the [H+] of the solution. If the solution is acidic, the ratio [In-]: [HIn] will become low. The indicator will therefore show predominately colour A (acidic colour).

On the other hand, if the solution is alkaline,the H+ ions furnished by the indicator will be taken up to form unionised water.There will be a larger concentration of the ions In-.The indicator will therefore show predominantly colour B(basic colour).

Phenolphthalein is a colourless weak acid.It dissolves in water and dissociates to some extent. HPh H+ + Ph(colourless) (colourless) Pink Phenolphthalein, or any other indicator,first undergoes a reversible tautomeric change into a substance of a different colour which then ionises almost completely to give the coloured anions. HPh HPh* H+ + PhConc. of the undissociated molecules is usually very small.

If the solution is acidic, the H+ ions furnished by the acid suppress the dissociation of phenolphthalein (common ion effect).The solution therefore remains colourless. In th presence of an alkali, the hydroxyl ions combine with the H+ ions furnished by the indicator to form unionised water. The solution therefore turns pink. The indicator appears colourless in acid and pink in alkali solution.

The reason why phenolphthalein is not a suitable indicator for titrating a weak base,like NH4OH,against a strong acid is that the OH- furnished by the weak base at the endpoint of the titration are too few to shift the eqbm. Sufficiently towards the right to raise the pH value to 8.3,at least and therefore, pink colour does not appear just at the end point. A sufficient excess of the weak base has to be added to get the pink colour.

Action Of Methyl Orange.

Methyl Orange is a weak base which may be represented as MeOH.It dissolves in water and undergoes dissociation to a small extent. MeOH Me+ + OHYellow Red Colourless If the solution is acidic,H+ ions furnished by the acid combine with OH- ions furnished by the indicator to form unionised water.

In acid solution this indicator gives red colour as more of the red coloured Me+ are formed. In the presence of an alkali the OH- ions suppress the dissociation of methyl orange.Hence the solution in alkaline medium remains yellow in colour. Methyl orange cannot be used as indicator for titrating a weak acid like acetic acid against a strong base because the H+ ionsfurnished by the weak acid at the endpoint are too few to combine with a sufficient number of hydroxyl ions of methyl orange to shift in favour of the red coloured Me+ ions.

Acid-Base Titrations and use of indicators:The process of acid base titrations is accompanied by a change in pH.A plot between pH of the solution during titration and the amount of acid (or alkali) added from a burette is called a titration curve. Indicators are frequently employed in detecting endpoints in acid-alkali titrations.

Since on account of hydrolysis, the pH value at the end point depends upon the relative strengths of the acid and the base being titrated and since different indicators have different pH ranges within which they can be used, the selection of a proper indicator for a given titration is very important.

Titration of a strong acid against a strong base:- HCl Vs NaOH Suppose,25ml of 0.1 N HCl is to be titrated against 0.1N NaOH.The end point will evidently occur on the addition of 25ml of the alkali solution. The pH values of the solution at different stages of neutralisation are plotted graphically as in fig against the increasing amounts of the alkali added. It is seen that the pH changes very slowly at first and rises from 1 to only about 4 when such a large amount as about 24.99 ml of the alkali has been added. Further addition of such a small portion as 0.01 ml of NaOH raises the pH value by about 3 units to pH 7.The acid is now completely neutralised.

Fig.

Further addition of such a small portion as 0.01 ml of NaOH will amount to adding free OH- ions and the pH value will jump to a value above 9.Thus near the endpoint, the titration curve is almost vertical and there is a rapid change of pH from about 4 to 10. An indicator is suitable only if it undergoes a change of colour at the pH prevailing near the endpoint. There are a number of indicators which can undergo colour change within the pH range 4 to 10.Thus any of them(Methyl orange/red,phenolphthalein) may be used to detect the endpoint while titrating a strong acid Vs strong base.

Titration Of weak acid with a strong base:CH3COOH Vs NaOH It is seen that the vertical portion now does not begin until beyond pH 7 and the endpoint lies somewhere between pH 8 and 10. This is due to the hydrolysis of sodium acetate which gives excess of OH- ions. Hence phenolphthalein will be a satisfactory indicator but not methyl orange or methyl red.

Titration Of a weak base with a strong acid:NH4OH Vs HCl Fig.

The pH of NH4Cl lies in the acid range,due to hydrolysis.The pH change at the endpoint therefore lies in the range 6 to 4.Thus methyl orange and methyl red are useful indicators while phenolphthalein cannot be of any use. Titration of Na2CO3 vs HCl It shows two inflection points. Na2CO3 + HCl NaHCO3 + NaCl ( pH 8.5) NaHCO3 + HCl NaCl + H2O +CO2(pH 4.3) Methyl orange is highly suitable indicator in this case.