Chapter 7 | ACID-BASE THEORIES Introduction During eighteenth century substances were classified into acids ang bases depending upon their properties like taste, soapy touch, change of the colour of litmus paper, reaction with limestone etc. In 1783, Lavoisie; Suggested that acids are binary compounds with one of the elements or oxygen. But in 1810, Davy stated that acids are the compounds Containing “H’ with a group of other atoms. Further support of the hydrogen theory of acidity was advanced in 1838 by Liebig who regarded acids as compounds containing hydrogen which could be replaced by metals. The present day views on acids and bases is traceable to the theory of “Electrolytic dissociation” proposed by Arrhenius. Many concepts on acids and bases have been proposed each being applicable only to a particular range of compounds. The following are the important acid-base concepts, ( Arrhenius Concept (Water System Concept) : In 1884, Arrhenius suggested theory of electrolytic dissociation for acids and bases. According to Arrhenium concept, an acid is any hydrogen containing compound which produces H* ions (or better HO ions) in aqueous solution and base is any compound which produces OH ions in aqueous solution. Compounds like HCl, HNO;, CHyCOOH ete. are acids as they produce H" ion in aqueous solution. H,0 Hel Hci. H* ions get hydrated by water and form hydronium ions H;0* H'+H,O = H,O* Compounds like NaOH, NH,OH ete. are bases as they produce OH” ions in aqueous solution.1B hase Theories jit! 0 Neon 22 at OFF jon can be On the basis this concen, acid-base neutralisation a ced by snsidered 28 a reaction involving combination of H* and OH” produ ine dissociation of the acig And base respectively to form H,0. N+ on — Ho n Application of Arvhenius Concept With the help . Attheniug Concept, we can explain the following 1. Aqueous so) lutions of oxid at S 1-1 etc. are acidic a8 they produce jy ions Fa a non ‘metals (SO;, SO,, CO, etc.) : eee 80, = 80, ayy soz 2. Compounds |i 0, NO are baa NH NSH and agueois Solution of metallic oxides like CaO, Na3O are basic as they Produce OH ions in water C20 + H,0 CaM), C224 2044 NH; +H,0 = NHOH os NHS+ on” 3. Neutralisation of, acid by base in 7 with the help of this concept, @queous solution can be understood 4. Quantitatively, strength o} f an acid and bi i ve : ase can be terms of ionization or dissociatio, Semen N Constant in Aqueous solution, HA+HO o H,O*+A- «= HO “ [HAI[H,O} - Since water is in large excess, concentration of water does not change (approximately 55 M) _ 0 1A] ___ Ha] Therefore K Limitations of Arrhenius Concept L(According to this concept, acidic and basic property is dependent only on its aqueous solution. \For example, hydrochloric acid is an acid only in aqueous solution but is Mot considered as acid in gaseous state, 2. It does not explain acidic and basic character in Non-aqueous ‘Olvents, For example, NH,NO; in liquid NH, acts as an acid though it does lot give H* ions,174 - 3, Neutralisation reactions are limited to a neutralisation reactions do occur in non-aqueous so] fae Solution of solvents or in the gas phase. For example, forms 284 even; MY. combination of NH) and HClig) cannot be explained. «°F NHS . + = 7 4! NHyq)+HChyy = eC by 4, It could not account for acidic character AICI; in aqueous solution. College Inorgay nie ¢ shown by the Salts, si (II) Lowry-Bronsted Concept (Protonic Concept) Lowry and Bronsted in 1923 proposed a broader and bases. It does not require Solvent participation’ Acéorg; © aci and Bronsted concept, an acid is a proton donor ‘and eine 10 Loy . acceptor. 5 Se is a oto For example, HCI—> H* + CI- : HCI loses one proton to give CI" ion, hence it is an acid. Si accepts the proton and hence is a base. Cl +H*—> HCI On the basis of Lowry and Bronsted concept, acids and bases m; | cationic, anionic or molecular. Some typical examples of these acids ' bases are given in Table 7.1. aa Concey milarly, cp Table 7.1 Bpe Bronsted acid Bronsted base | Molecular acid HX = x HNO, = -2H" 2- H,SO, — SO; HCIO, = HS +2H" H,O a OH”Theories pase it? Bronsted ac ‘y" : — NH} io ‘ H,0* wie HPO, HSo; HS- During an acid-base reaction when an acid loses a proton, its residual patthas a tendency to regain th. ‘ © Proton. Hence, it acts as a base. Therefore, general equation can be given, as Acid = yt 4 Base Proton Consider ionization of acetic acid in water CH,COOH + H,0 H,0* + CH,COO- Acid Base Acid Base Inthe above Teaction, conjugate base eg., HCI+NH, = NH} + cr Acid Base Conjugate Conjugate acid base In the above equation NH; is conjugate acid of base NH; and Cr is Conjugate base of acid HCI, Some other examples of Conjugate acid-base pairs are: ® 0+ co? —. HCO; + OH A B CA cB L conj, acid-base pair—! conj. acid-base pair(ii) Similarly ; rte cy, HCI+CH;COOH CH, COOH + ¢ me ie CA | a | LL _— con), acid-base pair B a - cconj- acid-base pair Strength of Bronsted Acids and Bases ; The strength of acid and base is expressed by yj; basicity constant or ionization constant K, and K, ne Using it b TESPective, - S acig; solution. ly inclly an G aque Consider an example of hydrofluoric acid in aqueou: eOu5 'S Solu HF + H,0 = H30{%q) + Fug) _g - BOLI ‘a [HF] [H,0] where. K, is dissociation constant of an acid. Since water is in large excess. _ HOU FI ‘a [HF] : ~ (1) If value of K, << 1 it means proton is not released by the acid very easily. Experimental value K, for HF in water is 3.5 x 10% which means under normal conditions only small reaction of HF molecule deprotonated in water. Hence, HF is a weak acid. Similarly, for a base like NH, accepting a proton can be given in terms of equilibrium constant, the basicity constant K, NH g(a9) + HO — NHj + OHG,) tion; a (2) Therefore, x, — NHL 10H] 7 [NH] (Water is pre: ent in large excess) : - IfK, << 1 base is a weak proton acceptor and hence it is 4° ein 1 of proton takes plac toprotolysis. base. Since water is amphoprotic solvent, transfe absence of acid or base, i.e., autoionization or aunl .G) Theories 0 Hy8joq)* OHfon . “KY TH,04 [0H] value of Ky is 1.00 « 4 ly small , at This shows that on of H,0 molecule jg Dresey ‘ 298K. This sh i “ ‘ ae Ntin Water . autoionization Constant helps to determine acidic or basic strength in ais conjugated acid ang bage, Thus, value of K, for NH, in water is . 6 yon’ Nu, + ho ts NH} +0H + 7 k= SHOW] (NH) ‘Action at *quilibrium can be given as: NH gi aq) + Ho, = HO) +NHy,, , (4) kK {H,0°}tNH,] _KK,= (Hoy fonp= K/ (5) 2 From the above ‘Telationship, it is Clear that, smaller the value of K,, larger will be K,. This Means stronger the base weaker is its conjugated acid. Following Conclusions can be (i) For Conjugated acid-base Pair, if acid is Strong, its Conjugated base will be weak. Similarly, if acid is Weak, its conjugated This means strong acid. base will be strong, weak base and weak acid-strong base pairs are allowed, drawn from the above facts. (ii) Reaction between Strong acid-base will proceed completely towards Tight and weak acid and base will be produced. But when wi feak acid and base react, no forward reaction will take place HCI+H,O = H,O'+cr strong — strong. weak ed acid base acid oo s "+ CHC CH,COOH+H,O = H,0 ae weak song ston er base acid — .-~Coleg tn, ‘Acids and bases can be classified as Weak of ni. constant. Values of acidity constant ton ee Che Table 7.2. Or some ag, tig 178 value of acidity solution is given 7 Table 7.2 \ Formula HA Acid ion + Name of the acid Hydriodic ul I Ion Pk, Perchloric HClO, ClO, Ig10 ii Hydrobromic HBr Br i i Hydrochloric HCI cr to? 4 sulfuric 11,80, HO; 10? ? Hydronium ion 11,0" H,0 1 2 Chloric HCIO, ClO; lo"! 0 Sulfurous H,S0, Istge | Hydrogensulfate ion HSO; 12 «192 1a) Phosphoric H,PO, 15 «199 2 Hydrofluoric HF 35x10 2 Carbonic H,CO, 43 «107 o Hydrogen sulfide HS 91 104 ayy Borie B(OH), B(OH); 12x10 914 ‘Ammonium ion NH} NH, 56x10" 935 Concept (Electron Pair Acceptor-Donor Concept) fundamental concept of acid-base behaviour vas in 1923. Later this concept was elaborated anf .o-workers. Lewis concept is widely used because (II) Lewis ‘Amore general and proposed by GN. Lewis extended by him and his c of its simplicity. Lewis defined acid as a substance from other substance and form coordinate covalent bond. Similarly, baseis defined as a substance which can donate an electron palt and form coordinate covalent bond. In other words/acid is an electron pair accepior ital 10 and base is a electron pair anes acid should have a vacant orb accept the electron pair donated by the base. For example when NH, reacts with BF;, boron ac from nitrogen of NH; and form coordinate covalent is an acid and NH, is a base. : which can accept an electron pat cepts electron Pat | Therefore, Bfpave Theories i F b Nu [ r + 3 , \ vemeealt “Benn, F F 179 basis of Lew; ; son wa a dinate gs ae the process of neutralisation is the tion OF a lent Fi M sation Product catteg adder! between an acid and base to form “NU can be considereg a wl alice? Reaction between H* roton) S Neutra n between H* (p aw ON reaction, } + NH; —, H ' qu 3 Nn, he, NHy ‘ Adduct Lewis concept does Not di: &r froy indkectton pair (Lewis base) jg Capable o inh aoe © of donating prone, Proton acceptor (Bronsteg base), 1 a te nena Pai to a theories are identical as far as bases are gre bases on the basis of Bronsted as well Concept with Tespect to : must ‘contain atleast ctron pair from a wis base, Lewis (i) Molecules con, molecules like PCI, SF,, atital and they readily accept electron adducts. Hence, they are Lewis acids, orbitals: In has vacant ‘gr is base and form deficient molecules like BE;, Lewis bases. Hence, they are Lewis acids, Lewis acid Lewis base Adduct BB+ OGH) > EB <0GH,) CAL + NCH; > CLAL NCH, (ili) Molecules having | clectronegativity, 8, CO>, SO, etc. In these molecules, oxygen is more Slectronegative than C or S atom. Hence the x electron density in the molecule is shifted more towards ‘O”, ie. away from C or S, Hence, C or S atoms Teadily accept electron Pair from Lewis base and form hiner . i i tial Lewis acids. e.g,, (iv) Simple cations: All simple Cations are bees ae slices mine complexes (adducts) are readily formed by CH (Lewis acids) with Lewis bases like NEG. multiple bonds between atoms that differ in180 . > College tp, or 8 Lewis Lewis nj acid ase Adduct “ Shey Ag + 2NH) > [HN > Ag enn! My 3. NH ‘ l mu Cu+4NH, > /HN > Cue NH L 3 NH, Lewis Acid Strength of Simple Cations ; Lewis acid strength of a cation is its tendency to a pair donated by the Lewis base. Thus, Lewis acid oe the Clecty, coordinating capacity witha Lewis base, i.e., ligand. The le 4 Cation ig Pa S acid strep, ith depends on the following properties of the cation. (i) Ionic radius of cation: Smaller the cationic radius tendency to accept electron pairs and hence stronger is is Lens is ity strength. Thus, the Lewis acid strength of cations increases for the Es oe ‘on moving from left to right ina period and from bottom to top ae Sroup of periodic table eg. H'>Na‘> K* (Cation of the same group) Li’ Ha eng : . ‘i jone pairs increases, their base strength decreases, |-© wt . tral (ii) Lewis base strength also depends upon the size of the cet ee om. As the size of central atom in a molecule increases, the eee to ihe central atom gets diffused over a larger region. Hence, the ability Ch donate the lone pair to a Lewis acid decreases, i.e., Lewis base strengt decreases, €.8., Among the hydrides of N, P, As, Sb and Bi, the Lewis basic strength decreases in the order NH; > PH, > AsH, > BiH. Advantages of Lewis concept (i) Lewis concept is more general than Bronsted protonic concept. (i) The concept includes the reactions in which protons are not involved. (iii) Acidic and basic properties of non-metallic and metallic oxides can be explained. (iv) Many high temperature, non-solvent reactions are included under neutralisation reactions. (v) Lewis concept is of great importance in some reactions where protonic concept is not applicable, e.g., reaction between acidic and basic oxides in the fused state, Limitations (i) The relative strengths of Lewis acids and bases cannot be explained. For example, experiments proved that fluoride complex of Be2* is more stable than that of Cu’* suggesting that Be°* ions are more acidic than Cu2* ions. But ammiine complex of Cu2* is more stable than that of Be2* indicating that Cu?* is more acidic than of Be?*. (ii) Acid base reactions should be fast reactions. But many Lewis acid-base reactions are slow. @) Solvent Solute System (Autoionization) Concept Solvent solute system concept was putforth by Franklin (1905) and was extended by Cady-Esley. They gave more general definition which could be applied inall cases where solvents undergo selt-ionization. According to this concept, the substances which when dissolved in a solvent form cations characteristic of that solvent, i.e., increases the cationic characteristicCollege organ; similarly, substances which "© Chem tic of that solvent or ii When dis. " nereases gy Mea 182 » called acids. led bases. For example, co ni > Consi ion der soy” solvent are form anions characte of the ina solvent, charac speristics of the solventare call H,0 for which the characteristic cation and anion ar 2 avely: e H,0° Ne respectively: and ge W,0+ 10 > H,0° + OH acid base acid base Thus, all those compounds which give H,O* ions in solv OH7 ions are bases. ent HO are which give acids and those ; The autoionization of some protonic and non-protonic solv be discussed as follows: ents can @ Autoionization of water can be represented in three ways. Acid Base (a) H,0 ee Ht + OF (6) 2H,0 = H,o* + OW (c) 3H,° = 2H,O* + oz H¢ or H3O° ions act as to solvent solute system concept, solution and OH and O2- ions behave as base. Therefore, Ht or H,0* ions in water behaves as an acid. ; According acids in aqueous HCI which gives Water HI = Ht+cr = 4H,0*+Cr | in three ways: HCI+H,O = an be presented i or (ii) Autoionization of liquid ammonia ¢ Acid base (a) onH, <= NM * NHz Amide @) 3NH, <= 2NHat NH Imide © ANEh = BNHE+ NT Nitride hich give NHj are acid, and substances W' ja solvent, jons are bases. In liquid ammon! NH, or N- which produces NH2,jon-Pr pase Theories eo ‘ protonic and eid The autoionization of some sven in Table 7.3. ‘i Table 7.3 eid + Ba | tipeof Solvent Sotont == eid * Ba Fons sles aoe ; @uo = Ht + 0H (21,0 = H,0° + OH 60 EE (3,0 = 2H OL LO. Gi) Liquid ammonia: (@2NH,, = NH; + NH> (6)3NH, = 2NH] + NH? (© 4NH, = 3NHP+NY ii) Acetic acid: . 2CH,COOH == CH,COOH; + CH,COO™ [ Non-protonic solvents 280, <2 sO*+S0> 2N,0, = 2NO* + 2NO; 2BrF, = Br} + Br, Advantage of Solvent Solute System Concept The concept helps to explain acid-base reactions occurring in aqueous and non-aqueous solvents which may be protonic or non-protonic. Limitations: 1. Acid-base behaviour is limited to solvent solute system only. It does not explain acid-base reactions which occur in absence of solvents. 2. This concept concentrates more on ionic reactions and on chemical properties of the solvents. It ignores the physical properties of the solvents. 3. It cannot explain neutralisation reactions occurring without the presence of ions. Hence, this concept is useful only when ionic reactions takes place. It cannot be used for the solvents which do not produce ions. (V) Lux-Flood Concept The concept proposed by Lux and extended by Flood is called Lux- Flood acid-base concept. This concept explains acid-base behaviour in tems> Iorganj, According to Lux-Flood concept, acid is q stoop oxide ton and base ia substance that donates oxigg e yp acid is oxide ion acceptor and base is oxide ion donor. This ace In mee js introduced to treat non-protonic systems which cannot be eS" Lowsy-Bronsted concept. For example, a high temperature reaction ined h Voli 184 College F he snyide ion" " of “oxide ion oie m ase molten oxides is CaO + SiO) = CaSiO, Base Acid CaO is oxide ion donor (CaO = Ca** + 07), Hence jx SiO, is oxide ion acceptor (SiO, +O” = SiOs”). Therefore, it ise bag Sid as an acid. ee Similarly, PbO + SO; = PbSO, Base Acid Lux-Flood concept has only a limited scope. It is limited mo: ‘ stly t systems involving moltem oxides. Y 10 the wn Hard and Soft Acids and Bases — HSAB Concept — Lewis acids and bases are classified into hard and Soft acids ang bases, ie., HSAB concept. HSAB principle is based on the. preferential bonding betwee metal ion and ligands. Ahrland, Chatt and Davies (1958) categorized the metal ions and ligands into two classes. (@) Class (a): This class includes ions of alkali metals, alkaline earth metals, lighter transition elements in higher oxidation state like Ti*+, Cr*, Fe™*, Co”* and H*. These ions have small size, possess high polarising power and are more electropositive. Their outer electrons or orbitals are not easily distorted. The ligands which preferably combine with these metal ions are also placed in class (a), e.g., NH3, RN, H,O and F etc. (ii) Class (6): This class includes ions of heavier transition metals _ and those in lower oxidation states such as Cu", Ag*, Hg”, Pd* and Pr”. These ions have large size, less polarising power and are less electropositive. Their outer electrons or orbitals are easily distortted. The ligands which preferably combine with class (b) metal ions are also placed in class (). e.g., the ligand R (phosphines) and R,S (thioethers) prefer to combine with Pd*, Pt?*, and Hg”*, which are the class (b) metal ions. Ahrland, Chatt and Davies have suggested that class (a) metal en which are more electropositive tend to form their most stable compe with ligands favouring electrostatic bonding. The stabilities of tl complexes with halide ions decrease in the following order.- - itive rocr> Bre less electropostt . which are ith ligan' IS onthe other hand, class (b) metal ions , exes With Tee jog ratively filled orbitals form most S@BI° OM Nit inaddition to possessing lone pairs of electrons cae “ailable € ACCoMMOdate some charge from the 4-01 ‘eer ret of tility is the reverse of that for class (a) metal increas abilities of class (b) met complexes with halide ions should in lowing order. exes. The e in the F, [Co(CN),P> Ce, Lu CO,, SO, |> College Inorganic cy, emis, In 186 Table 7.5: Classification of bases (R = alkyl or aryl group | Hard bases Soft bases | Bordertine by, } = "e bases } oN SC ; | NH. RNH3. NoMa | 1, CN*, SCN* S05 Br.NOs, sop | 1, RS, R,S, CO. CHAN. c BI SHANK, | 4,0, ROH, R,0 | on, NO}, ClO. co} | Hy BaP, POOR), po}, CH,COO cr | tt Pearson suggested a simple rule to predict qualitatively the i stabilities of complexes. According to him, hard acids prefer to bing bases and soft acids prefer to bind with soft bases to form complexes, id . This is Pearson's, principle. and soft acids and bases can be illustrated by th e The concept of hard 1 Lewis acid-base reaction. 32 | so} following A + :B — A:B Acid Base Complex - B is most stable when A and B are either both sof: The complex A - acid and base or both hai one of the reactants is very base. rdacid and base. The complex is least stable when hard acid or base and other is very soft acid or Pearson’s principle is only an approximate qualitative prediction of the relative stabilities for the complexes and is not a theory or any explanation of the observations. Theories of Hard and Soft Acids and Bases Several explanations have been put forward to provide theoretical basis to Pearson’s principles of hard and soft acids and bases. ; (i) Ionic and Covalent bonding: According to this concept, hard-hard interactions involve ionic bonding and soft-soft interactions result in covalent bonding. It is expected that small sized and highly charged metal ions should favour ionic bonding with hard bases of class (a). Miscono and his co-workers (1967) have developed an equation which correlates hardness and softness. pK =-logK + aX +BY+Y where, K is instability constant of the complex, X and Y are metal ions, 0 and B are the parameters of the ligands. The paramete for adjustment so that all pK values lie on the same scale. For hard the value of Y is found to be < 2.8 and for soft acids > 3.2. For border! parameters of JY is acids, ine187 yse Theories B increases from Fi f ithe value ranges between 2.8 and 3.2. The value 0 2.49, Br = 5.58: vase 10 SON Base, e.g, ON = 9.4, NH, = 1.08, Cl = en (ii) r-bonding: Mulliken il interaction on the basig of 6 have loosely held d-clect mab Ic ligands, having empty jaar (exept CO) helps to Applications of HSAB Concept — Pearson’s principle finds many scful applications, ined soft (1955) and Chatt (1956) have carne T-bonding, According to this theory, the to Tons which can form n-bonds by donating orbitals. The presence of d-orbitals on the Strengthen the n-bonding. SA HB Similarly out of the two cot Unstable i mplexes [Cd(NH,),]°* and [Cd(CN),P, the latter is expected to be more stable because both Cd?* and CN> are soft acid and soft base respectively. (ii) Occurrence of minerals: Hard acids such as Mg?*, Ca?* and AP* occur in the nature as MgCO,, CaCO, and Al,O, respectively. This is because cations (acids) and anions (bases) are both hard. These cations (acids) are never found in nature as sulphides since S*- is a soft base. On the other hand, soft acids such as Cu’, Ag" and Hg"* occur as sulphides. The border line acids such as Ni2*, Cu? and Pbe* occur in nature as carbonate and sulphides. . (iii) Poisoning of metal catalysts: Soft acids like Palladium and platinum Which are good catalysts are easily poisoned by soft bases like carbon Monoxide, olefins, ligands containing phosphorus or arsenic. Thus, carbon Monoxide and olefins are strongly absorbed on the surface of the metal and block the active sites. But these catalysts are not affected by hard bases Such as F, O, N ete.ie College Irorgain ic i ., me oy (iv) Course of chemical reactions “mh 1. W'+CHHgOH = 1,04 CHy Hg! UH CHHgSH = HLS+ CH gt | On the basis of HSAB concept I (a) reaction I should move towards right as hard acid He: with hard base OH>. Is SObinng (b) reaction II should move towards left as the SOR acid ¢ g combining with soft base SH, CHotiys is Lil + CsF = LiF + Cs} This reaction should easily move towards Tight as . ; Soft Cs+ to combine with soft Ir and hard Lit Prefers hard f- a Prefers (v) Relative strength of hydracids of halogens: HX+H,0 = H,0*+X°(X=R,C1, Br, 1) Hard acid H* combines Teadily with har HF. Hence, in-aqueous solution, the reaction with HF does not Move readi, towards right and therefore HF is weak acid. Therefore, the Strength Hs hydracids of halogens in the order HF < HCl < HBr < HL. d base F- and forms stable Application of Acid-base Concept In acid base titration In acid base titration neutralization reaction involves determination of amount of acid or base required for complete reaction of acid or base. This Point is known as equivalence point or theoretical end Point which involves indicator. The end point of acid base depends on pH. pH of the solution which depends on concentration of analyte and titrant. A graph of pH vs. volume of titration is known as neutralization curv e or titration curve pH during the titration can be theoretically calculated which is used in the Construction of titration curve. ‘7-Ponstruction of Titration Cu rves and Choice of Indicators: (1) Titration of a Strong Acid and a Strong Base: . Let us consider a simple titration of 10 cm? of 0.1 M HCI with 0.1 M NaOH. We can calculate the pH on adding a known volume of NaOH as follows:y- oir base Theories (i) At the start of titration: ° Cone, of HCI = 0.1 M a TH} =0.1 = 19-1 "A pRS ival equiv: (ii) When 5 cm of 0.1 M NaOH has been added (half eq! ; : 0 point) there will be S cm? of unneutralised HCI in a total volume 5). (104 lence 3 “THT =5 x a = 0.0333 PH = ~ log [H*] log [0.0333] = 1.48 . PH = 1.48 (iii) Vicinity of equivalence point When 9.9 cm? of NaOH has been added 9.9 cm of HCI will be neutralised and the total volume will be 19.9 om3. Unneutalised HCI will be 0.1 cm}, 01 (H] =01x T9.9 75025 x 104 PH =~ log [H*] =~ iog [5.025 x 10] = 3.30 (iv) When 10 cm? of NaOH has been added (at equivalence point.) The HCI solution will be completely neutralized, the solution will be neutral since acid and base are Strong and pH of the solution will be 7.0. (¥) When 10.1 cm? of NaOH has been added 0.1 cm? of NaOH will be in excess in a total Volume of 20.1 cm} 0.1 r= =4: 04; [OH] = 0.1 x 20,1 74975 *1 POH = — log [OH"] =~ log [4.975 x 104] =3,3 -. pH = 14-33 = 10.7 (vi) When 11.0 cm? of NaOH has been added 1 cm? of NaOH will be in excess in a total volume of 21.0 em? +. (OH]=1x a = 4.76 10°; pOH=2.3 . pH=14-2.3=11.7 It will be seen from the above results, that in the beginning pH rises Slowly but when 9.9 cm? to 10.1 cm? of NaOH has been added, the pH a the solution jumps up from 3.3 to 10.7. That is, in the te of the equivalence point, the rate of change of pH is very rapid. (Fig. 7.1)M8 Inoryan, oy hi 190, In the ease of 0.1 M solutions of acids and bases, the mm, the vieinity of equivalence point is 3.3 10 10.7. ‘Thererar® BI cha © an : Used 16 deg Micatoy which changes its colour within this rang rs end point. The equivalence point of this titration oceuy at pH 7. such as bromothymol blue or phenol red which changes Colour at, 7 would be apropriate. In actual practice, phenolphthalein and aoe bi are also suitable indicator. Phenolphihalein change colour fre to pink at pH range 8.3-10.0 indicating that end point will be clout om’. Addition of just one drop (0.05 cm? or less ) Of the base be to 19, equivalence point (pH 7) is thus sufficient to change the co the phenolphthalein. Methyl orange changes from red to yellow at pH OUr of 3.1-4.4 indicating that end point will be close to 9.9 cm. (ig 7, range 14 14 13 12 11 10 9 x= a 8 7 6 5 4 3 2 1 0 10 12 14 16 18 20 alkali added cm’ Fig. 7.1: 10 em HCI with NaOH of the same concentration191 cories ase The — Indicator ranges Thymol phthalein ~ " Phenol red ph RoR A ® Bromorhymol blue 10.0 404 10.2 alkali added cm? In Friedal Craft Reactions _ Alkylation In Friedal Craft alkylation alkyl halide with aluminium chloride as a Lewis acid Catalyst is used, In this process AICI; enhances the electrophilicity ofthe alkyl halide, Other Lewis acids such as BF,, FeCl,, sed. During the alkylation the alkyl halide react form a a more electrophilic caron a carbocation, Th can be explained with the help of following mechanism. Step 1: The alkyl halide reacts with the Lewis acid to form a more slectrophilic'C, a carbocation. ZnCl, canalso be 'S with the lewis acid to Step 2: Loss of the halide to the Lewis acid forms the electrophilic alkyl carbocation.Ss 192 College Inorganic Che Step 3: The p-electrons of the aromatic C=C act ag 5 “Me attacking the electrophilic C+. This step destroys the aromeya,” vent cyclohexadienyl cation intermediate. Heity givin Step 4: Removal of the proton from the spre bearing the reforms the C=C and the aromatic system, generating HC! tg the active catalyst. : Tar "eReneray in AICI, —AIC! ~) Acylation: In Friedal Craft acylation reaction acid chloride are used to attach the RCO- acyl group to the aromatic ring in presence of strong Lewis acid catalyst, e.g., AICI, oO a Ar—H+R—C atch ama Cl ‘acid chloride Oo ketone The Friedal Craft acylation involves following steps. RCOCI+ AICI, ——> RC = =, 0° + AICI; basejd-base Theories qi ATH+RC H a +Alcl, COR acid, > Ar—C—R+HCI+AIC, es I ketone This reaction is acid Catalysed nuc! aromatic ring acts as leophilic acyl substitution and ee leophilie. Fri lation is important method for Preparing ketones, pt Tiedal Craft acylation i IpO! (1 Questions 1. On the basis of ) Atthenius the terms acid “oneept and (i?) Lowry-Bronsted. concer 3, explain and base With suitable examples, mem ~ Gi) HCO; (ivy PO; 2 > 3. What do you understand examples, 4. Discuss brie! advantages? © HI+H0 = Horsey (ii) ‘NH, + HCI = NH} +Cr - On the basis of (i) solvent system Concept explain the terms acid and base with Suitable examples, = ~ What is Lewis concept of acids and bases? Explain with Suitable examples, 8. Differentiate between Bronsted and Lewis concept of acids and bases with Suitable examples, 9. What are the different types s of Lewis acids and bases? Classify the following as Lewis acids and bases: ()Ag* (ii) BF, (ii) F (iv) Zn?* (@) AICI, 10. Differentiate between: (@) Bronsted concept and Lewis concept of acids and bases, (6) Hard and soft acids and bases., College Inors Banic Chy Memisr, 4 11. Explain the following (i) Relative ctrength of Bronsted acids and bases. (i) Pearson's principle of hard and soft acids and bases. iin) Coniueate acid-base pai 12, Write notes on (9 HSAB Concept (ii) Strength of acids and bases on the basis of protonic concept, (iii) Electron pair acceptor-donor concept and its advantages, 13. How will you construct curve in stron acid and base titration? 14. How is acid have concept used in Acylation? 15, Explain use of acid base concept in alkylation. (I) Short Questions Multiple Choice Question 1, An acid is a compound that gives OH ions in water. 7 ¢ gives H* ion in water and base isa Q « his concept was given by aes (@) Amenius (b) Lewis \S Lowry 2. A substance that accept proton according to Bronsted-lowry concept is (@) anacid ) base (©) a neutral substance 3. In following reaction H,O+HCIl> H,O* + Cr + species which acts as a base is (@) H,0 (b) HCI (9 40° 4, A molecule or ion that can behave both as Bronsted acid and base are called (a) mono protic acid (b) amphiprotic acid (©) poly protic base . According to Lewis concept an acid is acceptor. (a) prot , )) proton )) electron pair (©) base . 6. HCO, isan example of (a) conjugated acid (b) amphiprotic ion (c) conjugated baseit ge Theories he | AL nen and molecule that are Short of an electron pair act as (a) Lewis acid (b) Lewis base oO Bronsted bases inthe reaction between NH, and HCL Hcl+ NH, = NH} + cr ‘The conjugated acid of NH, is @ Re ((b) NH @a Weak base has conjugated acy vrisiaed base’ ated acid and weak acid has eed increases the electrophilcity of the alkyl halide ee (©) AICI, (© HNO, - Alkyl halide reacts with the lewis acid and forms electrophilic (@) anion (63 fearbocation (©) carboanion . Friedal ccraft acylation is important method of Preparing (a) alcohol (b) benzene © ketones 90002ualitative Analysis compl 7 13, Discuss With suitable examples the ae : ions, i a 1e What is. ‘onic strength? Discuss its relation with et in qu e “plain with suitable examples common ion ef CD Short Questions (@) Fillin the Blanks ev 1. Identifi a : ication and finding out the constituents : sis * Tons with negative charges are called ” ide are Carbon Dioxide, Sulphur Oxides, Nitic Acid, Hydrogen Chieti ‘gases, 6. Ifa glowing splinter reli is i . ights again, then the gas is ; i | 7 IF the evolving gas extinguishes a splinter and the gas burns with @ PoP sound then it is | 8. The confirmatory test for Chlorine is___test. The colour of Bromine gas is 10. The colour of Iodine gas is ; 11. The formula for Potassium Dichromate is. 12, Dimethyl Glyoxine paper is used to test_____. 13. Ammonium Chloride and Ammonium hydroxide have a____ion. 14. To maintain constant pH a mixture is used. 2 Qoo0o0°0tes ened Ry OF AHI at NaCI, NaOH, C#0, CHO ten oF OR. nitrogen with respect too seannencteal sepeTS cm Semester It - Paper ' 21 Concept of Qualitative A i Gascon: peotknes, Rome of Papers mer erated with Reagents reference (0 fnpreanated with starch Teenethylahyorinne ane tine (ny) Testin sn nal anestysis (09 jndide, pemtmceite™” dicho, Jead acetate. ) (py Precipitation equilibria effect of com FOR. amcommon ions, oxidation antes, bniffer action, comphexine agents 0m precipitation of ionic compounds (Balanced chemical eqprations: ‘and namerical problerns ) 2.2 Acid-base Theories (8L) Arthenits. Lowry Bronsted. Lewis, Solvent — Solute concept of acids and axes, Hard and Sofl acids and bases. ‘Applications of HSAB Applications of acid istry in: @ Understanding. organic reactions like Friedel Craft's (acylation/alkylation) reaction Gi) Fae wa gc foe win ESS involving strong ‘acid and strong bast. semester Il — Paper Il (Unit Il) 2.1 Chemical Bond and Reactivity (7L) Types of chemical bond, compari ionic and bonds, polarizability (Fajan’s Rule). ‘of molecules, Lewis dot structure, Sidgwick Powell Theory, basic eek theory for ABs type molecules with and without lone pair of electrons, isoelectronic principles, applications and limitations of VSEPR theory. 2.2 Oxidation-Reduction Chemistry (8L) (a) Reduction potentials (b) Redox potentials: half reactions; balancing redox equations: (c) Redox stability im water (i) Latimer and Frost Diagrams (ii) pH dependence of | ‘redox potentials. (@) Applica’ of redox chemistry (i) Ex : ates un of elements: (example: isolation of copper by auto reduction) ( ; KMn0. ieee ge ce ems a Fe(ll)); and (b) Multi ccm ame ss in Kaas a