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10 Modern Concepts of Acids and Bases

10.1 INTRODUCTION
Our recognition o f som e chem ical substances as acids and certain others as bases w as based on som e experim ental facts. A cids and bases possess in a sense opposite characteristics. A cids and bases have been identified by their effects on som e organic dyestuffs. For instance acids turn blue litm us red while the bases change red litmus blue. A cids counter the effect o f bases and vice versa. Som e acids ev o lv e hydrogen when reacting with som e metals. W ith the availability o f large experim ental data there arose a need to define acids and bases on a rational basis. The concepts o f acids and bases developed one after another tend to make the definitions more and more broad based. Here w e w ill discuss the various concepts o f acids and bases but with special em phasis on their m odem concepts.

10.2 ARRHENIUS CONCEPT-THE WATER IONS SYSTEM A ccording to Arrhenius theory o f ionisation, all substances which give hydrogen ions when dissolved in warer could be called acids while, those which ionise in water to form hydroxyl ions, could be called bases.
Exam ples o f Arrhenius acids are HCl, H 1 SO 4 , CH 3 COOH. etc. Exam ples o f Arrhenius bases are N aO H , NH 4 OH, etc. A cid-base equilibria could now be treated in a quantitative w ay and acid-base neutralisation could be considered to result from the union o f the hydrogen ions with hydroxyl ions to form water m olecules, H + + O H ' ------ > H 20 When w e write a general equation. H A ------ > H+ + A ' for an acid, suggesting the formation o f a group, H*, but this is not very correct as free protons could exist only when gaseous hydrogen atoms are ionised. In the presence o f protophilic liquids such as water, unattached proton could not exist; in water a proton gets attached to a number o f water m olecules by co-ordinate linkages, releasing a very large amount o f energy. The proton in its hydrated state is usually . expressed by H iO \ even though the number o f water m olecules attached to one proton is more than one. The hydrated proton is called the h ydroxoniura or h yd ron iu m ion . On the other hand hydroxyl ions are also hydrated in water through hydrogen bonds and are represented by OH- formula only because o f convenience.

Successes
(i)

(ii) (iii)

Arrhenius concept has been invaluable in elucidating the behaviour o f aqueous solutions. The constant heat o f neutralisation o f a strong acid by a strong base is readily explained in ' the light o f this concept. This theory correlated the catalytic action o f acids with the concentration o f hydrogen ions. This concept also leads to quantitative determinations o f acid o r base strengths from the determination o f follow ing equilibrium relation :
K =

at r aB~ a HB

Limitations
(i) The Arrhenius concept lacks in generality. (ii) The most serious limitation is that it deals with dissociation and acidbase reactions in

aqueous medium only and does not mention the role o f non-aqueous solvents in the dissociaC o p y rig h te d m aterial

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tion o f acids and bases into ions. According to this concept, HCl is regarded as an acid only when dissolved in H 20 and not in some other solvents like benzene, chloroform, etc. or when it exists in the gaseous form. (iii) This concept restricts bases merely to hydroxides. Thus, even metal oxides w ould not be regarded as bases. (iv) According to this concept, a neutralisation process is restricted to aqueous medium alone but m any non-aqueous solvents like liquid NH 3 liquid SO 2 . etc. are known to undergo com parable acid-base neutralisation reactions. (v) It cannot explain the acidic behaviour o f certain salts such as AlCly in water. (v i ) This concept does not elaborate the fa te o f dissociated hydrogen ions in solution because o f their high hydrational energy (1075 kj/mole). (vii) A proton (H*) is non-existent and is generally present as the hydrated HxO' ion or species. (v iii) A prcton is also fo rm ed in other solvents like N IIj. ROH, etc. (ix) There are nonprotonic and nonhydroxylic compounds which may yield H y or O f f ions in water. S O , + H20 -> H 2 SO 4 & H+ + HSO 4
CaO + H20 Ca(O H ) 2

&

Ca2+ +

20H "

10.3 BRONSTED-LOWRY CONCEPT : THE PROTON-DONOR ACCEPTOR SYSTEM


Bronsted and Lowry in 1923 proposed a new concept to acids and bases w hich is independent of solvents. A ccording to atom.

An acid is any hydrogen contained substance ( a molecule o r a cation o r an anion) whereas a base is any substance (a molecule o r cation or an anion) that can accept a proton from any other
su b sta n c e .

From the above definition, it follow s that an acid is a proton donor am i base is a proton acceptor. It also follow s from this definition that it is not essential for bases to have OH" groups as dem anded by the Arrhenius theory. A neutralisation process, therefore, involves a release o f a proton by the acid, and the acceptance o f that proton by a base. This concept makes acid-base reactions also to be known as protolytic reactions independent o f solvent. ! I H : Cl + . N H 3 -> C P +
add have

NHa H20

NH j
acid

OH -> N H j +
base

Bronslcd and Lowry acids and bases are o f the follow ing types : B ro n sted -L o w ry acid s M olecular : HCl Cationic A nionic H ' + Cl"

:[A ( K ,0 )6 f * - H* + [A (H 2 0 ) 50 H ]2+ :H2POJ - H* + HPO;

B ro n sted -L o w ry b ases : M olecular : Py + H+ JPyHj* ; wherePy = Pyridine Cationic A nionic : [A (H 2 0 ) 5 0 H ] 2+ + H* : PO ^ + H r H P O | [A(H 2 0 ) 6 f +

Subsjances like H 20 and H CO j ions w ho donate as well as accept protons.

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373

H 2O H 2O + H 4 ^ HCO 3 HCO 3 + H+ ^ arc classed as am p h o teric substanccs The Bronstcd-Lowry concept (i)

H+ + OH" (donation) H 3 0 + (acccptance) H* + C O f (donation) H 2C O 3 (acceptance)

is quite useful For example:

This concept also takes into account protonic solvents like NH ^H iSO ^, etc. NH? + NH3 & NH4 + NH2
H2SO4 + H2SO4 i * H3SO4 + HSO4

(ii)

A ll proton transfer reactions may be treated as follow s : N Hj + S2' -> NHi + HS"

C o n ju g a te A cid s an d B ases : A study o f the follow ing reactions for processes occurring in water brings out another important feature o f this concept about acids and bases : CH 3 COOH + OH H20 + H 20 & HOH + C H 3 COO" H3 C + + OH"

NH.; + CO2'
H 20 + C O !' r f

HCO- + N H ,
H C O j + OH

From the above reactions, it is seen that when a m olecule or an ion loses a proton, it is necessary to convert into a form w hich would accept a proton, to reform the original acid. The latter form is therefore, a base and it is called a linked or co n ju g a te b ase to the initial acid. S u ch p a irs o f su b sta n ces w h ich a re fo rm ed from o n e a n o th er by th e g ain or loss o f a p ro to n are called co n ju g a te acid-base pairs. A cetic acid and acetate ion, H 2 O and OH" ion and NH 4 ion and N H 3 , H 3 0 + ion and H 2 O, HCO 3 ion and CO 3 " ion are all exam ples o f conjugate pairs o f acids and bases. Just as for every w eak acid w e have a conjugate base, for every weak base w e have a conjugate acid which is formed by the addition o f a proton to the base. The strong acids and bases are not covered by this statement for the lack o f the corresponding proton com bination. Furthermore, a substance like H N O 3 behaving as an acid or a base depends on the solvent uses. In liquid N H 3 , H 2 O and even dry C H 3 COOH, H N O 3 acts like an acid by donating protons, but in dry H F m edium , it accepts protons, and behaves like a base. R ela tiv e S trea n g th o f A cid s an d B ases. A ccording to Bronsted concept, the strength o f an acid is regarded as a measure o f its tendency to donate proton. Thus, a strong acid is that one which has a strong tendency to donate a proton. Sim ilarly, a strong bases is that one which has a strong tendency to accept a proton. Generally, two m ethods are em ployed to compare the relative strength o f given acids. These are as follow s : (i)

In the fir s t m ethod we com pare the dissociation constants o r ionisation constants o f acids/bases to get idea about their strength. Higher the dissociation constant, greater the strength o f acui/l)ase. For example, we are interested in comparing the acidic strength o f CHyCOOH and HCN. The values o f dissociation constant o f CH^COOH and H C N are 1.8 x 10* and 4.0 x 1010 respectively.
CHjCOOH + HjO HCN + H20 ^ HiO* + C H ,C O O '(K ,= ! 8 x !0~5) H ,0 * + CN~ (Ka = 4 0 x 13~')

A s the value o f Ka o f C H 3 COOH is greater than that o f HCN, it means that C H 3 COOH is a stronger acid than HCN and CN" ion is a stronger base than C H 3 COO" ion

>py righted

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M O D E R N C O N C EPTS O F A C ID S A N D BASES

(ii)

The second method is known as competitive protolysis method. In this method, one acid is added to the conjugate base o f another acid, and, then, one has to determine the equilibrium concentrations experimentally. For example, ifN a O C iH 5 is added to Ih O , it is exprimentally fo u n d that Cihl$0 ~ has good tendency to react completely with the H 2 O to from CihhOH and OH ion. It means that C 2 H 5 0 ~/s a stronger base than 0H~ o" d H 2 O is a stronger acid than C 2 H 5 OH.
H2 O +
S tronger acid

C 2 H5Cr ^
S tronger base

C 2 H 5 OH +
W eaker acid

0H

W eaker base

It is important to mention here that acidity increases with the increase o f positive charge whereas the basicity increases with the increase o f positive charge. Thus, [Fe(H 2 0 ) 6]*+ is a stronger acid than [Fe(H 20 )6 l2* ion and [N i(O H )4]2" is a sironger base than [Ni(OH)4r ion.

Successes
(i) (ii)

(iii)

This concept shows that acid base phenomena are dependent on the solvent. The concept covers a large number and variety o f substances under base, fo r example, hydroxide ion, amide ion, ethoxide ion, pyridine, alcohols, acetate ion, bisulphate ion and m any others. Bronsted-Lowry concept is useful in accounting fo r the hydrolysis o f salt solution. A solution o f FeCli is acidic because the proton donor ability o f hydrated ferric ion exceeds the proton acceptor aoility o f the chloride ion and measurable excess o f [F eiH iO jJ** ion appears in the solutions.

FeClj + ,(H20 &

[FihH,0)J1t + 3CI'

L im ita tio n s : This theory serves excellently in protonic solvents but fails in case o f som e obvious acid-base reaction. For exam ple, the formation o f H 2 SO 4 by the reaction o f SO 3 and HoO, the acidic participant S O 3 in this case has no protons to give.

10.4 LEVELLING SOLVENTS


The apparent strength o f a protonic acid has been found to depend upon the solvent in which the acid is d issolved. W hen all the acids which are stronger than HjO+ (e.g., HC 1 0 4 , H 2 SO 4 , HCl and HNO 3 ) are added to H 20 , they lose a proton to H 2 O forming H 3 O* ion. All these acids have equal strength because all these acids have been levelled to the strength o f H^O* ion which remains in solution and is com m on to all such solutions. This phenomenon in which the strength o f all the acids becomes equal to that o f H jO + ion is known as levelling effect o f the solvent i.e., water. Here water is known as a levelling solvent for all these acids. S olv en t H20 [ c 2HsOH A cid H 3 0*(H B r) C 2H 5 O H * (HBr) + Base K*. Br" K+. Br Salt + 2H 20 2C 2 H5OH S olven t

O H '(K O H ) 0"C 2H , (KOC 2 H5)

T he solvents in w hich com plete transfer takes place are known as levelling solvents. It means that the solvents in w hich the solute is 100% ionised are known as levelling solvents. For exam ple, liquid N H 3 acts as a levellin g solvent for H F and HCl because both these are -100% ionised in liquid N H 3 to g iv e ~ 100% N H j ions. In H 2 O, H F undergoes partial ionisation w hile HCl and HBr undergo -100% ionisation. Thus, H ;0 is a differentiating solvent for HF but for HCl and HBr it is a levelling solvent. Other solvents m ay have their ow n levelling effects, too. Thus, benzoic acid is a very weak acid in aqueous solution. But in liquid ammonia it acts as a very strong acid. In general, it may be expected that acidic solvents (like acetic acid) w ill exert less levelling effect on acid strengths (and sim ilarly-basic solvents on base strengths). Relative strengths o f the com m on mineral acids have been obtained by conductace measurement in anhydrous acetic acid. The order found is HCIO 4 > HBr > H 2 SO 4 > HCl > HNO 3
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SOLVENT SYSTEM CONCEPT


franklin extended the dissociation principles to non-aqueous solvents and realised that non-aqueous solvent m olecules may also dissociate into two oppositely charged ions. A ccording to him , if an acid releases 1-T in water to form H 3 O* ions then an ammonium salt, NH 4 CI, by releasing NH 4 in liquid am m onia, must also be termed an acid. If NaOH. by virtue o f its releasing OH ion in aqueous medium , is termed a base in that medium , then N aN H 2 should also be termed a base in liquid N H 3 since it releases the am ide, N H 2 ion. The dissociation (or auto-ionisation) o f non-aqucous solvent is responsible in such solvents. NH3 ^ H+ + N H 2 A ccording to Franklin, an acid is a substance which by dissolution in the solvent fo rm s the same

cation as does the solvent itself due to autoionisation. A base is one that gives on dissociation in the solvent the sam e anion as does the solvent itself on its own ionisation.
S o lv en t H 20 C>H5OH ...... A cid + H 3 0 + (HBr) C 2H 5 O H | (HBr)........ B ase O H '(K O H ) O X 2 Hs (KOC 2 Hs) S alt + K+, Br~ K+, Br S o v en t 2H 20 2C 2 H5OH

The solvent system concept to non-protonic solvent e.g., S 0 2, COCl 2 in case o f acids and bases w as applied by Cady and Elsey. A ccording to them, substances which increase the consentration o f the

cation characteristics o f the solvent are acids, whereas substances which increase the concentration o f the anion characteristics o f the solvents are bases.
In N 2 0 4 as a solvent, substances such as NOC1 which yield N O + ions behave as acids, and substances such as N aN O j which yield N O 3 ions behave as bases. The auto-ionisation o f som e non-protonic solvents is given below : A cid Base S02 + S02 ^ A cid Base SO + + SO]~ COC1COC1J+ c r 2NO" + 2 N 0 5 BrFj + BrFi

C O C h + COCl 2 ^
N 20
4

+ N 20

BrFj + BrF?

Just as with Arrhenius concept neutralisation is reaction between an acid and a base to produce a salt and the solvent. Neutralisation reactions in non-aqucous media are given below : Acid In liquid N H j : NH4Cl + In liquid S 0 2 : SO C l 2 + Base N aN H 2 N a 2S 0 3 Salt Solvent NaCl + 2N H 3 2NaCl +
2 SO 2

It is clear from the follow in g reactions that there is com plete analogy between solvolytic and am photeric behaviours in aqueous and non-aqucous solvents.

Solvo/ytic behaviour

In liq. NH j : A lC h + N H j -> [A K N fy )]2* + H* + 3CI In H20 : A lC lj + H20 -> |A I(O H ))2t + H* + 3CI

Am photeric behaviour : In liq N H 3 : Zn(N H 2)2 + 2N H 2 In H 20 : Zn(OH ) 2 + 20H " [Zn(NH 2)4}2' [Zn(OH) 4 J2

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Success
This genera! iheory o f solvent system concept possesses the obvious advantage o f relating acid-base behaviour in aqueous and non-aqueous solvents, both protonic and nonprotonic.

Limitations (i) It limits acid-base phenomena to solvent systems only. (ii) The concept does not explain the neutralisation occurring without the absence o f solvent. (iii) It does not explain the acid-base processes which may occur in the absence o f solvent. (iv) In low dielectric constant solvents, the existence o f ions is not attainable. (v) Emphasis has been laid mainly on the chemical properties o f the solvent. However, the physical properties have been completely ignored. (vi) Too much stress has been laid mainly on the ionic reaction which actually even dielectric affects would be able to explain the reactions easily. For instance, Gutman and his coworkers (1952-60) have explained reactions between the chloride ion acceptors (FeCly.SnClj, etc.) and chloride ion donors (Me^NCl ) in OPCl$ as follows:
OPCI 3 Me-tNCl ^ OPCI 3 + FeC ! 3 OPCI2 + C P M e 4 N + + Cl~ 0PC1J + F cC i; (autoionisation) (base) (acid)

H ow ever, M eek and Drago (1 962) show ed that the reaction can be carried out equally w ell in triethyl phosphate m edium without involving chloride ions. It means that the dielectric constant o f the m edium is m ore important than the ionisation reaction o f the solvent. Thus the solvent system concept for acid and bases sim ply extends, but d oes not necessarily im prove, the Arrthenius waterions system .

10.6 LUX-FLOOD CONCEPT


Lux proposed a theory to explain the acid-bases concept o f oxide system . A ccording to the concept,

a base is any m aterial which gives up oxide ions and an acid is any material which gains oxide ions.
Som e tyical reactions are Base ^ Acid + xO z~

s o jCaO

&
p*

SOj + O2'
Ca2 + 0 2

H ence according to the concept, a bases is an oxide donor and acid is an oxide ion acceptor. This view is particularly useful to high temperature chemistry, as in the fields o f ceram ics and metallurgy. For exam ple, the follow ing reactions CaO + S 1 O 2 * CaSiOj PbO + S 0 3 -> P b S 0 4 involving basic oxides (CaO,PbO) and acidic oxides (SO*. SiO?) arc reacting to form salts. Furthermore, according to this theory amphoteric substances are those which show both a tendency

to take up or give up oxide ions depending upon the circumstances, i.e.,


Na20 + ZnO -> 2N aT + ZnOjS" Acid The oxid e transfer picture due to Lux can be extended to any negative ion, i.e., halide, sulphide, etc. 3N aF + A F , - > 3 Na< - + A lF - temperature 0 The L ux-flood definition can be extended to include transfer o f any anion e.g., halide, sulphide, etc.

Limitations
The lim itations o f such a concept are abvious. This view can be reduced to one part o f the more general theories o f L ew is and Usanovich.

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10.7 CADY-ELSEY CONCEPT


Bases on the characteristic cation or anion o f the solvent which is produced by it with the solute, a more general definition o f acids and bases applicable to all solvents w as provided by Cady and E lsey. Consider, for exam ple. (i) (ii) (iii) (iv ) (v) H20 + H20 -> H jO + + OHT

N H 3 + N H 3 -> NHJ + N H i HF + HF -> H 2 F t + F" N 2C 4 + N 20


4

-> 2N O + + 2N O j CH 2COOH5 + C H 3COO"

CH 3 COOH + CH.iCOOH

The characteristic cations furnished by water, am monia, hydrogen fluoride and nitrogen tetroxide from (i). (ii), (iii) and (iv ) above are respectively H?Or, NH4, H 2F* and NO* . The respective characteristic anions o f these solvents are O H ', N H 2, F " and N O 3 . A ccording to C ady-Elsey concept :

An acid is a substance which in dissolution in solvent gives the cations characteristic o f the solvent and a base is a substance which yields anion characterstic o f the solvent either by direct dissolution or by reaction with the solvent.
In the light o f this concept, it is seen from (i), (ii), (iii) and (iv) above that : A ll substances which furnish H 3 O ions in water solvent, NHJ ions in am m onia solvent, H 2 F f in hydrogen fluoride solvent NO* in nitrogen tetroxide and acetic acid medium are termed as bases. For exam ple, NH4X & NH 4 + X~

in ammonia is an acid and M N H 2 - - N r N H 2 in it is a base. BF 3 in hydrogen fluoride reacts as BFj + 2H F I-bF* + BF4 forming H 2 F+ ions. It is therefore an acid.

10.8 ELECTRON-DCNOR-ACCEPTOR SYSTEM OR THE LEWIS CONCEPT


Gilbert N. Lew is proposed a broader concept o f acids and bases that liberated acid-base phenom ena from the proton; although L ew is first proposed his system in 1923, he did little to develop it until }938, L ew is defined a base as a substance that has an unshared electron pair with which it can form a covalent bond with an atom, molecule, o r ion. A n acid is a substance that can form a covalent bond by accepting an electron pa ir fro m a base. An acid must have a vacant orbital into w hich an electron pair donated by a base can be accommodated. An exam ple o f a L ew is acid-base reaction that is not treated as such by any other acid-base concept is :F : H I I F - B + :N- H I I :F : H
A cid (acceptor) B ase (donor) (E lcctrophilc) (N u d co p h ile )

:F: H I I :F - B < N - H I I :F: H


_ . o m ^ CX

Lew is acid is often described as acceptor o r electrophile, and the Lew is base is called a donor and nucleophile. On the basis o f this concept, cations arc acid-base com plexes. in C la ssifica tio n o f L ew is acid s and bases : Based on the L ew is system are essentially the sam e as Bronsted-Lowry system , since any molecule or ion which accepts protons does so because o f the

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presence o f an unshared pair o f electrons. For exam ple. OH , Cl . NH.v H 3 O*, CN" etc., arc bases on
ihe L ew is as w ell on Bronsted-Lowry system .

The properties o f an acid might be due to the availability o f an empty orbital fo r the acceptance o f a pa ir o f electrons. Hence L ew is definition does not attribute acidity to any particular elem ent but
rather, to a unique electronic arrangement. A ccording to this concept, acids are classified as : 1. M olecu les p o ssessin g a ccn tral atom w ith less th an a n o ctet o f electron s. L ew is acids o f this class are the electron deficient m olecules such as B in B F i, A1 in AICU. F F F B+ :NH< F B : NH, F / F '
Acitl (accep to r) (E lcctro p h ile) Base (donor) (N uclcophilc) C om plex

2. M o lecu les in w h ich th e cen tral atom has a v a ila b le d* orb itals a n d m ay acq u ire m ore than an o ctet o f valen ce electro n s. Silicon tetrafluoride and tin (IV) chloride are typical exam ples :

SiF 4 +
L ew is acid

:F
base

SiF 6~ ; SnCl* +
C om plex Lew is acid

2 : C 1 S N C l ^
Lew is base

2-

L ew is

C om plex

Som e other exam ples o f this type are : P F .i. P F s , TcCI 4 ,SF 4 , ScF 4 , TiX 4 , GcX 4 , These halides tend to form adducts with a number o f organic bases. C a tio n s : This class o f Lewis acids is made up o f positively charged heavy m etal ions with incomplete stable orbitals. 'i*heoretically, all cations arc potential L ew is acids because they are electron deficient. H ow ever, this property is negligible for the alkali metal cations such as N a \ and K+, and is w eak for the alkaline earth cations such as Ca2+, Sr2+ and Ba2*. O f the alkaline earth group, only M g2+ and Be~+ show an appreciable tendency to behave as L ew is acid. The reaction o f M ,H type o f ion with water m olecu les is an exam ple o f Lew is acid-base interaction. 3. h 2o 6H 20 . . Acid Base (where M = Al, Cr, Fe) M h 2o OH 2 1 ^ o h T oh oh2 com plex
2

T he reaction o f A g + with NH* is also typical : A g+ +


L ew is acid
2

: NHj
L ew iz base

[H jN A g : N H 3r
C om pelx

U sually, the number o f reacting nucleophiles is tw ice the charge on the cation. 4. M o lecu les w ith a m ultip le bond b etw een atom s o f d issim ilar electro n eg a tiv ities : An exam ple o f such a m olecule is carbon dioxide, O = C = O. The oxygen atoms are more electronegative than the carbon atom. A s a result, the electron density due to the it electrons is displaced aw ay from the carbon atom, towards the oxygen atoms. The carbon atom is electron deficient and is apt to from a bond with a L ew is base such as OH' OH * 6 : O = C = O : + : ' 6 H - ------>
6

Lew is acid

Lew is base

:O

0 :

bicarbonate Ion

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S O 2 reacts like C O 2 towards O H - .

5+

5 o
A xo

o - s = 0 : + :o h
OH Bisulphite ion 5. E lem en ts w ith an electron sextet : O xygen and sulphur atoms contain six electrons in their valency shells and, therefore, act as Lew is acids. The oxidation o f sulphite to SOr" by oxygen , and to S2O v by sulphur involves acid-reactions.

: 0 + so l

(o<- so.02 "


so3)2~

: s + so?" -> (s
Successes
(i) (ii)

(iii) (iv)

Lewis concept is a broader interpretation o f acid- base behaviour. This theory is not dependent on the presence o f one particular element, upon any given combination o f elements, upon the presence o f ions, or upon the presence o r absence o f a solvent. The Lewis approach is, however, o f great value in case where protonic concept is not a p plicable. Lewis theory is frequently employed to interpret reaction mechanisms.

Limitations
(i)

(ii)

In Lewis approach there is a lack o f uniform scale o f acid and base strength. The strength o f acid and base in terms o f Lewis concept is variable and dependent on the reaction con sidered. In this respect it is inferior to Arrhenius concept or the Lowry concept. The concept is so broad that it is unsuited to general chemistry', in which the explanation o f acid-base behaviour is most important o f an acid.

10.9 USANOViCH CONCEPT (POStTIVE-NEGATtVE SYSTEM)


U sanovich proposed definitions o f acid and bases which are m ost com prehensive o f all acid -b ase theories given from time to time. A ccording to him, an acid is any species capable o f giving cations, combining with anions o r electrons, o r neutralising a base to yield salt. In a similar w ay he defined base

as any species capable o f giving up anions or electrons, combining with cations, or neutralising an acid to yield a salt. The U sanivich theory includes all precious acid - base definitions and in this process it
has becom e too general. It also includes oxidation-reduction reaction as a special class o f acid - base reactions. U sanovich has placed considerable em phasis on the central atom in the com pound w hile accounting for the acid-base character o f a substance. By co-ordination unsaturation he m eans the ability o f an atom to increase its covalence. The acid function is determined by the presence o f co-ordinately unsat 11 rated positive particles while basic function by the presence o f similarly unsaturated negative particles. For instance, in S O 2 the central atom can be considered to be sulphur, and it is co-ordinately unsaturated. Thus, it is capable o f accepting an anion such O 2*, thereby acting as an acid. In general acidity is promoted by highly charged positive particles (N a 2 0 is highly basic while A 120 ^ is less basic) and basicity by highly charged negative particle.

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A cid base relation sh ip s on the basis o f U san ovich con cept. A cid C li SO* + + + Base Sail 2N a 2N aC l N a?0 3(N H 4)2S > N a 2S 0 4 - 2(N H 4 )*SbS 4 Justification Na loses an electron, C l, gains, an electron N a 2 0 yields O 2"
u p O" (N H 4 )2 S gives up S > 2Sb 2 S.s gains S'

Sb 2 S< +

Success
U sanovich concept is useful in classifyin g all exam ples o f acidity and basicity. It is m ost general for all other definitions o f acid-base so far given.

Limitations
Usanovich concept is o f great value fo r specific problems, but fo r general considerations, it is undoubtedly too broad to be o f wide applicability. (ii) The theory virtually involves that all chemical reactions fa ll into an acid-base category, and one begins to wonder at the purpose o f using any name other than chemical reaction. O th er th e o rie s : K onopic (1949) proposed donor-acceptor acids and bases which amount to little more than that o f U sanovich concept. B jerru m (1951) considered acid as a proton donor while a co n ventional L ew is acid be referred to as an antibase. M ulliken (1 952) developed quantum m echanical treat
(i) ment o f acids and bases. But all these theories add nothing new to our know ledge. A ctually w e may say that each approach is correct as far as it goes and no conflict exists around them. But one should know the main them e o f each concept and should adopt his thinking to the particular problem in hand.

10.10 SOFT AND HARD ACIDS AND BASES (THE SHAB PRINCIPLE)
Based on the preferential bonding, Arland, Chatt and D avies ( l 9 5 8 ) categorised the metal ions into tw o cla sses : 1. C la ss (a) . This includes ions o f alkali metals, alkaline earth metals, lighter transition m etals in higher oxidation states like Ti44, Cr3+, F eu and C o u , and the hydrogen ion. H+ T hese ions have the follow in g characteristic features : (i) fiii)

They have small size, high polarising pow er and high oxidation state. Their outer electrons o r orbitals are not easily distorted
:

1. C la ss (b) This includes ions o f the heavier transition m etals and those inlow er oxidation states such as C u \ A g \ H g 2 +, Pd2\ Pt2+, etc. These ions have the follow ing characteristic features (i) These are targe sized. (ii) Their outer electrons o r orbitals are easily distorted. D epending upon their behaviour towards the metals o f classes (a) and (b), the ligands have been categorised by Arland, Chatt and D avies into the follow ing two classes : 2. C la ss (a) : T his includes ligands which preferentially com bine with metal ions o f class (a) For exam ple, the ligands N H i, R jN , H20 and F" ions have great tendency to co-ordinate with class (a) metal ions. The tendecv o f the com plexation o f the ligands with class (a) metal ions follow s the order given below : F > C l> B r > I O > S > Se > Te N > P > A s > Sb

2. C la ss (b) : This includes ligands which preferentially com bine with metal ions o f class (b). For exam ple, ligands such as R^P (phosphincs) and RyS have great tendency to co-ordinate with class .(b) metal ions. The tendency o f the cc nplexation o f the ligands with class (b) metal ions follo w s the order given b elow :

A D V A N C E D IN O R G A N IC /

381

F < C l< B r < I O < S < N < P < Se = Te A s < Sb

Pearson (1 963) suggested that terms hard and soft can be used for class (a) and class (b) respectively. Thus, in his classification, metal ions o f class (a) arc called hard acids and ligands o f class (a) are called hard bases. On the other hand, metal ions and ligands o f class (b) are callcd soft acids and soft bases respec!ivcly. P ea r so n 's P rin cip le - The typical Lew is acid-base reaction can be generalized as A + ; B -------- A :B
L ew is acid (A ccep to r) L ew is base (D onor) C om plex

T o broaden the scop e o f the reactions we assum e that the bond in A B can be ionic, polar, or non-polar. It w ould be very beneficial if one could prcdict the stability o f the com plex A :B . A concept designed to explain it is called the principle o f S o ft and H ard acid s andb ases and was proposed by P earson (1 9 6 3 ). S o f t b a ses have d o n o r a to m s w hich are ea sily p o la rise d a n d w hich h a ve low electronegativity. These criteria arc interdcpcdcnt, although not absolutely equivalent. T hey each relate to the ease with which electrons can be distorted aw ay from the donor site. Hard bases have properties opposite to those o f the soft bases : the donor atoms tend to retain its electrons. Thus, hard bases have donor atoms with low polarizabilities and high electronegativities. Table 1 show s som e typical acids classified as hard, borderline and soft. Table 2 sh ow s som e typical bases classified ashard,borderline, and soft. W ithin a group in the periodic table, softn ess increases with increasing size o f the donor atom. Thus, o f the halide ions., F" is the hardest and I is the softest. Hard base is hard to oxid ize and so fi base is easy to oxid ize,

|
H a rd A cids H+,L i \ N a \ K +, < R b \C s+) : B e 2*.B e(C H 3 );M g3+, C a 2+,Sr 2 +B a2+

TABLE <1) CLASSIFICATION OF ACIDS


B ord erlin e A cids F c2\ C o 2*, N i2+, C ir*. Zn3* Rh-M r^ .R u *. B (C H ,)G aH ,
,

S o ft A cids C o (C N )^ , Pd2*. P i2*. P i4*

Cu*. A g+, Au*, C d2+. Ht;2* H g2+, C H .H g* BH i.G a(CH >)i.G aC li GaBrj.Ga T l, Tl (CHi).i,

S c 3 +.L a 1 X ,e 4 +,G du ,Lu3+, Th 4 +,U 4 +,U O f,P u 4+ T i4+, Zr4+, Hl4+, V 0 2+ C r \ C r6 \M o O u ,W 0 4f M n 2+,M n 7 +,Fe 3 f ,C o3+ BF 3 .B C l 3 ,B (O R ) 3 ,A l* \ AI(CH 3)3. AICI3 ,A1H3, G a 'M n * C 0 2, R C O +, N C \ S i4* Sn 4 +.C H 3 S n u ,(CH 3 )jSn2+ N 3*, R P 0 6*, R 0 P 0 2\ A s3+ s o 3. r s o ; , r o s o 2 c t \ c i 7 +,i 5 M 74 |H X (hydrogen-bonding m olecules)

R.iC*. C 6 H j, S n - , Pb2* N O +, Stv Bi'*

S02

CH^.carbenes 7i- acceptors : trinitrobenzene, chloranil, quinones, Tetracyanoe thylene, etc. HO+,RO*. RS+,R Se+, Te 4 *,RTc* Br2 ,BrM 2 .lM C N ,etc. 0 , C l, Br, I, N , RO", RO?.

M (metal atom s) and bulk metals Ij


------------ -----------

---------------------------------1

Soft acids arc those which have acceptor atoms large in size, o f low positive charge and containing unshared pa ir o f electrons (p o r d elcctorns) in their valence shell, i.e., they have high polarizability -nd
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M O D E R N C O N C E P TS O F A C ID S A N D B ASES

low clectroncgativity and do not have a noble gas configuration. Hard acids are those in w hich acceptor

atoms are sm all in size, o f high electronegativity and low polarizability and a noble gas configuration.

|
H ard B ases N H j,R N H 2 ,N 2 H 4

TABLE (2) CLASSIFICATION OF BASE


B ord erlin e B ases S o ft B ases H"

C6H5NH2 , C5H5N, NJ, N 2


n o *.

|h 2 0, OH". ()2 , ROH, RO-, r 2 o


CHiCOCT, C O }'. NO>,

soy-

R-,C2 H4,C6H6,CN-, RNC, CO SCN". RiP, (RO).iP, R2 As r2 s , r s h .rs '. s2 of r

Br

i HO]'. SOj-. CIOj 1F-. (C D

Soft acids form stable com p lexes with bases that arc highly polarisable, and are good reducing agents and not necessarily good bases towards the proton. Hard acids. On the other hand, usually form stable com p lexes with bases that bind w ell with protons. W e now apply the idea o f soft and hard acids and bases to the question o f the stability o f the com plex A : B The complex A B is most stable when A and B are either both soft o r both hard. The

com plex is least stable when one o f the reactants is very hard and the other is very soft.
Pearsons principle is only an approximate qualitative prediction o f the relative stability for the adducts and is not a theory or any explanation o f the observations. T h eo r ies o f H a rd n ess a n d S o ftn ess - Several theories have been put forward to explain the fact that the co-ordination com pounds o f soft acids and soft bases arc m ost stable. The various theories are : 1. E lectro n ic th eory - A ccording to the theory, hard-hard interactions involve ionic bonding and soft-soft interactions involve covalent bonding. It is expected that smallsized and highly charged positive metal ions w ould be favouring ionic bonding with hard bases o f class (a). If hard-soft interaction takes place, the resulting sp ecies would be unstable. M ison o and Coworkers (1 967) proposed the follow in g equation w hich correlates hardness and soft ness.

pK = - log K = aX + bY + c
w here K is the equilibrium constant for the d issociation o f the m etal-ligand com p lex, X .Y are the parameters o f the metal ions, a and b arc parameters for the ligands, and c is a constant o f the ligand to adjust the p K values so that all the values lie on the sam e scale. For hard acids, the value o f Y is found to he > 2 . 8 and for soft acid > 3.2. For border line acids, the value ranges betw een 2-8 and 3.2. For exam ple, the values o f Y are as follow s L if Ai*+ 0-36 0 70
H ard acids

M g2+ 0-S0

Na+ 0 93

K* 0 93 T l+ 3-78

Ca2+ F e * 1 6 2 2-32 H g2*

C o3* C s+ 2-56 2-73 A u+ 4-25

C o2+ 2-96

Sn2+ 3 17

T I * C u2* Pb2+ 3-2 3-45 3 58

5 95

Soft acids

Hie value o f b (ligand parameter) also increases as w e m ove from a hard base to a soft base. OH" 0 40 NH, 108 Cr 2-49 Br" 5-5 I~ 717 S 20?~ 12 4

It is interesting to note that a and X arc also regarded its another measure o f hardness. H ow ever, th ese include the inherent acid base strengths a lso X has been found to be c lo se ly related to the electronegativity o f the metal ion and is considered to be measure o f the tendency o f the m etals ions to accept electrons from the ligands. Further X follow s the sam e order as that W illiam s order for the stability constants o f the com p lexes : Mn (II) < Fe (II) < C o (II) < N i (II) < Cu (II)

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2. n B o n d in g th eory - J. Chatt's pi-bonding theory can b e applied to explain the bonding between
the soft-soft com p lexes. A ccording to this theory, the soft acids have loosely held outer d-orbitals electrons w hich can form p i- bonds by donating to suitable ligands. Such ligands are those in w hich em pty J-orbtials are available on the basic atom s, eg. P. As. S, I, etc. The presence o f d-orbital, on the ligands (except on C O ) helps to strengthen the it-bonding. 3. P itz e r 's th eo ry - This theory o f London and van der W aals forces explains that the forces betw een the interacting soft-soft groups depend upon the product o f poiarizabilities o f the interacting groups. Both soft acids and soft base have larges values o f polarizabilities. E lectro n eg a tiv ity an d H a rd n ess an d S o ftn ess - Hardness and softness have been found to be related to electronegativity. In brief, highly electronegative sp ecies arc hard acids w hile low er electrongativc sp ecies are soft acids. For exam ple, highly electronegative ions like Li+, Na*, etc. arc hard acids w hile transition metal ions having low electronegativities like Cu+, A g+, C u \ etc. are soft acids. A cid an d B ase S tren g th o f S H A B Any acid or base may be considered as hard or soft by its apparent preference for the hard and soft reactants. For instance, a base B is considered to be hard or soft depending upon the value o f equilibrium constant K for the follow in g reaction : BH+ + C H 3 H g+ ^ C h,H gB* + H f ... (1) BH+ -> B + H+ K = [CH.iHgB*] [H+] = [CHjHgB+J (CH.iHg4) [BH*]

[H+] (B]

- ... ...

(2) (3) (4)

[CH.OlHg4! [B] fBH 4] = Ks Ka or log K = log Ks + log Ka

If the value o f K is less than unity, B is termed as a hard base and if it is greater than unity, B is termed as a soft base. In equation (4), Ks denotes the formation constant o f CHiHgB* from C H 3 H g+ and B w hile Ka denotes the acid dissociation constant o f the conjugate acid BH+. From the values o f K and Ka, it is also possible to decide whether B is hard or soft. If pK a is more than log Kv, B is termed as hard base and if p K (t is less than lo g Kx, B is termed as soft base. From the equation (2), it also follow s that the reaction (1) w ill g o to the left if B is a hard base. H ow ever, it w ill go to the right, if B is a soft base. N o w the question arises : W hy methyl mercury (II) cation is selected in the above discussion ? The sim ple reasons for this are : (i) (ii)

It is a typical soft acid, It is univalent like proton, making the calculations simpler.

Hardness and softn ess are quite different from the inherent acid-base strengths because these sim ply rcler to the hard-hard and soft-soft interactions. For exam ple, both hydroxide ion and fluoride ion are hard bases. H ow ever, the hydroxide ion (w h ose pK<, is 15.7) is I0 1 1 tim es more basic than the fluoride ion (w h ose pK is 2.85). Certain exam ples are known in which a strong acid or base may displace a weak acid or base although this may violate the principle o f SH A B interactions. For exam ple, a stronger soft base sulphite displaces a weaker hard base fluoride from a hard acid proton :

SO?" + HF - HSO, + F , K, = I0J


Sim ilarly, a very strong hard base displaces a soft weak base from a soft m ethyl mercury (II) cation. OH" + C H iH gSO J - CH jH gO H + S O ^ ,K ,= 10 The above replacem ent reactions take place against the hardsoft principle. H ow ever, when both the strengths and hardness are taken into cansidcrations, the hard-soft rule works w ell. For exam ple, consider the follo w in w g reactions :

CH.iHgF + H.SC),-

-> C H .H g S O r + HF( K*,= I01)


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M O D E R N C O N C E P TS O F A C ID S A N D B ASES

C H 3HgOH + HSO 3 C H 3 H g S 0 3~ + H 2 0 ( K $q= 1 0 7) In ihe above reactions both sulphite (/?K3~ 14.2) and hydroxyl ion (pKa= 15.7) com bine with protons. But the /?KS for sulphite ions with methyl mercury (II) cation is 21.2 w hile in case o f hydroxyl ion is only 9.4 Therefore, sulphite is considered to be a soft base. A p p lica tio n s o f th e S H A B p rin cip le The principle o f soft and hard acid-base finds applications in various dom ains o f chem ical reactions. Som e o f them are : (i) T h e sim plest reaction that can be explained on this concept is L il + C sF -> LiF + C sl This is an exotherm ic reaction with 13.9 kJ/mole heat o f reaction. Here soft iodide prefers to com bine with the soft caesium ion. The hard fluoride ion com bines w iiii hard lithium ion. (ii) For heterogeneous catalysis, S H A B principle says that soft m etals adsorb soft bases. For solubility, the rule is that hard solutes d issolve in hard solvents and soft solutes d issolve in soft solvents. (iii) O c cu rre n c e o f m in era ls - The kinds o f metal ores found in the earths crust can be rationalized by using this principle Thus, hard acids such as Ca2+. M g2* and A l3+ appear as C a C 0 3, MgCO? and AI2 O 3 respectively. The anions C O }2- and O 2- are also hard. These three hard acid cations are never found as their sulphides sin ce S 2" is a soft base. H ow ever, soft acid such as C u * , A g + and H g2* are found to be com bined with the soft base S 2 as sulphides. The intermediate acids such as N i2\ Pb2+, and C u2+ are found as both sulphides and carbonates. (iv) In both BF 3 and B H 3 , the boron is trivalent but quite different behaviour can be explained on the basis o f S H A B principle. The presence o f hard fluoride ions in BF 3 m akes it easy to add other hard bases, eg. H 3 N > B F 3 . the presence o f soft hydride ions in BH 3 makes it easy to add other soft bases. In B F 3 the boron is nearly B 3* . But the soft hydride ions donate negative charges exten sively to boron, so that the boron atom is alm ost neutral and becom es soft. (v) For elem ents o f variable valency there is usually an increase in hardness with increase in oxida tion state. The nickel (0) in N i (CO) 4 is soft, m ickel (II) is borderine and nickel (IV ) is hard. (vi) The sulphur end o f the thiocyanate ion is assum ed to be softer than the nitrogen end, and hence prefers soft L ew is acids. (ii) R ela tiv e sta b ilities o f C o m p o u n d s B y using Tables I and II and Pearsons rule, it becom es p ossib le to explain the relative stabilities o f the com pounds and com plexes. For exam ple, Agl^ is stable, but A gF :d oes not exist. A s described earlier, A g+ is a soft acid F" is a hard base and I" is a soft base. Therefore, A gH (soft acid + soft base) is a stable com plex and can explain that CoF'l" (hard acid + hard base) is m ore stable than ColJ" (hard acid + hard base ). B y using the SH A B principle, it is possible to predict the relative strength o f halogen acids in aqueous m edium . For exam ple. H X + H 20 -> H 3 0 + + X ~ (where X = F , C l , Br or I) In the above reaction, the hard acid H + com bines with the hardest base F~ to form the dissociated or w eakest acid. Thus, the strengths o f the halogen acids w ill fo llo w the follow in g order : HF < HCl < HBr < HI
W eakest acid strongest acid

Out o f the tw o com p lexes, [Cd (NH 3) 4 ] 2* and [Cd (C N ) 4 J?~ latter should be more stable (com bination o f soft acid C d2T with soft base (C N " ) on the basis o f SH A B principle. (iii) P o iso n in g o f m etal catal ca ta ly sts. This has been explained on the basis o f S H A B principle. Soft m etals (e.g Pd and Pt) act as catalysts and they are easily poisoned with CO, olefin s, phosphorus or arsenic ligands (all soft bases). These ligands adsorb strongly on the surface o f the metal and block the active sites. The soft metal catalysts are not affected by hard bases such as F.O.N.

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385

(ix ) R ates o f ch em ica l reaction s. The S H A B principle has been used to correlate the rates o f chem ical reactions. The rates o f electrophilic anti nucleophilic reactions have been found to depend upon the hardness or softness o f the acid or base (x) C o u rse o f reaction s. The S H A B principle has been used to predict the course o f a reaction. Consider the follow in g reactions : H + + CH3HgOH -> H .O + CHjHg* (1) H + -f CH sH gSH -> H2S + CH 3 Hg* ... (2) A ccording to SH A B principle, the reaction (1) should m ove towards right because the hard acid H* is com bining with hard base OH" the reaction (2) should m ove towards left because the soft m ethyl mecrury C H jH g 4 acid is com bining with soft HS base. L im ita tio n s o f S H A B con cep t. The various lim itations o f this concept are as follow s : (i) (ii)

It does not involve any quantitative scale o f measurement. In order to explain the obsen'ed phenomenon, one has to break a compound to acid and base fragm ents. This breaking will be correct only i f the reaction is known. For example, the break I fo r the estenfication reactions explains the obsen'ed behaviour. However, the break II cannot be ignored and should be taken into consideration.
CH 3 CO+OH" + C 2 H 5 CTH* CH 3 COO"H+ + C 2 H}OH~ Break I Break II

(iii)

In this concept, it is assumed that hard-soft factors do not depend upon the acidic o r basic character o f the compounds and therefore tney work independently. However, many examples are known which show interdependence o f the two concepts. Due to the soft-soft ( C H f - H ) interactions, it is expected that the follow ing reaction should proceed.

(iv)

C H l(g) + H 2 (g) - > CH 4 + H+(g) H ow ever, the unfavourable entropy change (3 6 0 0 kJ m ole-1) indicates that this reaction should not proceed at all and the reason for this is that there is greater acidity o f the proton relative to the C H } nucleus.

Conclusion
T he hard-soft classification is a useful concept, but it docs not lead directly to a scale o f acid-base strength. Inherent acid-base strengths are also not taken into consideration. Thus the OH" and F" ions are both hard bases. But the former is nearly 10 13 tim es as strong a base as the latter. Various approaches to correlate inherent acid-base strength with attributed hardness (and softness) factors are yet to be w idely accepted. Interpretation o f many reactions by splitting the participants into acid-base fragments is also arbitrary to som e extent. The very com m on reaction between ethanol and acetic acid m ay be interpreted in either o f two w ays : CH,COO"H+ + C 2 H 5 + OH" or CH3CO + OH" + C 2 H 5 0"H* Either interpretation is justifiable by the hard-hard com bination o f H* with OH". The actual in vol vem ent o f the second m echanism has to be understood by other means. Som etim es the hard-soft principle fails to keep parity with inherent acid-base strengths. The reaction: CHJOf) + H2 fe) -> CH 4 (s ) + H +(g) should be favourable in v iew o f the soft-soft com bination o f C H t with H". But actually the com bination in endotherm ic by about 3 6 0 kJ per m ole. (This has to be explained by the greater acidity o f H* relative to C H *). Sim ilarly, hard-soft com binations take place in many cases like S 0 3J- + HF H SO j + F

386

M O D E R N C O N C E P TS O F A C ID S A N D B A SE S

Here the soft bane SOl~ replaces the hard base F SO? is thus stronger than the hard F

and com bines w ith the hard acid H*. The soft

H o w ev er, w e sh o u ld restrict o u r ex p ectation s in v iew o f th e sta tem en t m a d e by P ea rso n - "It

should be stressed that the SHAB principle is not o f theory but is a statem ent about experim ental facts. Accordingly an explanation o f some observation in terms o f hard and soft behaviour does not invalidate some other, theoretical explanation . "

10.11 STRENGTH O F HYDRACIDS


The relative strengths o f the hydracids o f Group VI A and VII A have been found to be as follow s: (i) H 2Te > U2S c > H 2S > H20 3 4 7 16 (ii) HI > HBr > HCl > HF -1 0 -9 - 7 3 T he above trend is also found in hydracids o f Group V A . For exam ple, the pKa for am m onia (35) is m ore than that for phosphine (27). From the above trend it appears that the strength o f the acid is decreasing with the increase in the electronegativity o f the elem ents. H ow ever, this trend is not found in the ionic character o f the bonds because the ionic character has been found to increase with the electronegativity o f the elem ent.

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