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5 Acids and Bases: The Arrhenius and LowryBrønsted Theories
The concepts of acid and base are central to chemistry as a whole. A vast majority of organic reactions are either promoted by acids or bases, or involve the participation of acids or bases at some stage of the reaction pathway. Moreover, the application of acid-base chemistry in organic chemistry is wide-reaching: unlike the other subdisciplines of chemistry, an overwhelming majority of reactions are carried out in media other than water. This means that the concepts of acids and bases must be applied to a much broader range of conditions than those that applied when most of us learned about acids and bases for the first time. However, let us begin by reviewing the definitions of acids and bases in aqueous solution.
Arrhenius acids and bases
The earliest operational definitions of acids and bases were related to the neutralization of acids by bases given by the relatively simple equation that follows (equation 1.6):
Acid + Base Salt + Water
This simple equation defines neutralization: the destruction of an acid by an equivalent amount of base to give a salt. The formation of the water itself comes from the neutralization process, a situation forst recognized by the great Swedish chemist, Svante Arrhenius. As part of his dissociation theory of electrolytes (that when ionic compounds dissolve in water the ions dissociate and become free to move within the solution), Arrhenius looked at electrolytes that were originally nonconductors, and proposed the first definition of an acid:
an acid is a substance which functions as a source of hydrogen ions in aqueous solution
on the other hand. but dissolve in water to give a strongly conducting solution containing hydronium (H3O+) ions. as the electronegativity of the element bonded to the acidic hydrogen atom increases. The ionic hydroxides of the Group IA and heavier Group IIA metals. NaOH and KOH are all widely used as strong bases. the extension of this definition to bases was relatively straightforward. more accurately. often labeled as "ammonium hydroxide" are actually best described as ammonia molecules dissolved in water. There are two structural features which one can use to predict the probable strength of an acid: the atom to which the acidic hydrogen is bonded. Instead. The pH of 1 M solutions of these acids is typically quite low ³ close to zero. In a similar vein. and so need only dissolve to dissociate and liberate their hydroxide ion. the pH of a 1 M solution of a weak acid is much more likely to be close to 2 or 3. on the other hand. hydronium ion) source in aqueous solution. Ammonia. All these acids are covalent when pure. with only a few percent being converted to ammonium and hydroxide ions. nitric acid (HNO3). hydriodic acid (HI). especially those of the Group IA metals. dissolve freely in water to give solutions containing high concentrations of hydroxide ions: LiOH.Once acids had been defined in this manner. much of a weak acid remains unionized in aqueous solution. Strong acids ionize (dissociate) completely in aqueous solution. hydrobromic acid (HBr). The functional definitions of strong and weak acids are still based largely upon the Arrhenius definition. but it does so without extensive ionization. and many are familiar to most students in chemistry: sulfuric acid (H2SO4). acid strength increases: O³H hydrogens are more acidic than N³H . hydrochloric acid (HCl). the strength of a base is related to the ease with which it functions as a source of hydroxide ions in aqueous solution: strong bases are good sources of hydroxide ions in aqueous solution and weak bases are not. Weak acids. and the number of multiple bonds between the central atom and oxygen in oxyacids. indicating a hydronium ion concentration only a few percent of that of a strong acid. Like the aqueous solutions of weak acids. Typical weak acids are compounds such as acetic acid (CH3COOH). Most of the strong bases commonly used in aqueous solution are ionic hydroxides that already have the hydroxide ion present. do not dissolve to give complete dissociation. dissolves extremely well in water. the Arrhenius definition of a base states: a base is a substance which functions as a source of hydroxide ions in aqueous solution The strength of an acid is related to the ease with which it functions as a hydrogen ion (or. and perchloric acid (HClO4) are among the more familiar strong acids. which ionizes only to the extent of a few percent in a 1 M solution. Ammonia solutions. aqueous solutions of weak bases like ammonia are relatively poor electrolytes. In general.
8 The transfer of a proton to a proton acceptor is an acid-base reaction under the Lowry-Brønsted definition. it does not fit well with the Arrhenius definition of an acid-base reaction. There are. The effects of multiple bonds between the central atom and oxygen atoms also appears to be cumulative: hypochlorous acid (H³O³Cl). and the ammonia.hydrogens. And yet. a salt. and not all acid-base reactions result in the formation of water. hydrogen iodide is the strongest binary (two-element) acid known. methyloxonium ion. Here. A more widely applicable definition of acids and bases is that due to Lowry and Brønsted. is one of the strongest acids known. which has no chlorine-oxygen double bonds. in turn. perchloric acid (HClO4). Since hydroxide ion is never involved in this reaction. the proton is transferred from a molecule of hydrogen chloride to a molecule of methanol to generate its conjugate acid. this reaction clearly leads to the neutralization of the hydrogen chloride. leading to the formation of the salt. a base is a hydrogen ion acceptor. For example. many cases where an acid-base reaction has obviously occurred. an acid is a hydrogen ion donor. but where no water is formed. In the Lowry-Brønsted definition. . the base. is a very weak acid. Figure 1. in fact. hydrogen chloride gas reacts with ammonia gas to form ammonium chloride. which are. who extended the Arrhenius definition of acids and bases to cover just such situations. which has three oxygen atoms doubly-bonded to the central chlorine atom. more acidic than C³H hyrogens. Acid strength also increases dramatically as the element to which the hydrogen is bonded becomes larger: although hydrogen fluoride is a relatively weak acid (pKa = 2). the acid. Lowry-Brønsted acids and bases Not all chemistry is carried out in aqueous solution.
H3O+. Nevertheless. by competition reactions in a non-aqueous . and a base. during the course of the reaction in Figure 1. All acid-base reactions proceed to give the weaker of the two conjugate acids and the weaker of the two conjugate bases as the products of the reaction. and is therefore the acid. as useful measures of the relative acid strength of a species in solution. we have retained the concept of the acidity constant. are required. and its negative logarithm (base 10). When a proton is added to a base. the conjugate base (chloride anion) is weak. the anion formed. Because of the frequency and importance of proton-transfer reactions in organic chemistry.7 is too limiting. for example. the pKa. Ka. The hydrogen chloride molecule is the proton donor.8: HA + H2O H3O+ + A- (1. The oxygen atom of the methanol molecule is functioning as the proton acceptor. A-. have been measured indirectly. for a strong acid such as hydrogen chloride (or hydrochloric acid). some familiarity with the concepts of acidity constant. the conjugate base (hydroxide anion) is strong.8) However. and is given in equation 1. the acid (hydrogen chloride) is converted to its conjugate base (chloride ion). H³ A. When a proton is removed from an acid.7) (1. Thus. Let us examine the case of a simple proton-transfer reaction between an acid. and is therefore the base. Many of these values for organic compounds. Thus. from water.A simple example of an acid-base reaction by the Lowry-Brønsted definition is the protonation of the methanol molecule by hydrogen chloride to give the methyloxonium ion. Ka.8. B-: . The acidity constant of a Lowry-Brønsted acid was originally defined in terms of its ability to form hydronium ion. however. As the acid (or base) becomes stronger. and we are now in a position where equation 1. the product of the reaction is termed the conjugate acid of the base. while for a weak acid such as water. HA. this definition is rather too narrow. is termed the conjugate base of the acid. its conjugate base (or acid) becomes weaker. while the base (methanol) is converted to its conjugate acid (methyloxonium ion). with the extension of acid-base chemistry into non-aqueous reaction solvents.
in turn more acidic than O³H bonds. (1. if the Ka of HA is greater than the Ka of HB). is a much more commonly used measure of acid strength. which was defined earlier as ³log10(Ka). . the conjugate base of water. the conjugate base of methane (CH4. Some typical pKaranges are given in Table 1.10.will lie to the right. which are. (1. the pKa.10) By multiplying both the numerator and the denominator of this expression by [H3O+].12 tells us is that if HA is a stronger acid than HB (i. The other measure of acidity. One consequence of this is that we can expand our view of acids and. CH3Li.HA + B. As the elementv to which the acidic hydrogen is bonded becomes larger.14) As pointed out earlier. pKa = 45-60). morte particularly. in turn. pKa = 35) and methyllithium. the conjugate base of ammonia (NH3. and that O³H bonds are more acidic than N?H bonds. Using pKavalues for the two acids. and as the electronegativity of the element bonded to the acidic hydrogen increases.11) Reorganization of equation 1. This allows us to observe that Se³H bonds are more acidic than S³H bonds and that S³H bonds are. are much stronger bases than hydroxide ion.13) (1. acid strength of a covalent compound varies with the element to which the acidic hydrogen is bonded. the acid strength increases. Stronger acids have an algebraically smaller value of the pKa than weaker acids. acid strength increases. (1.8.14: (1. It is worth repeating here that although the pKa scale was originally defined for Lowry-Brønsted acids in aqueous solution. the expression given as 1. Bases such as amide anion. bases. more acidic than C³H bonds.13 and 1.11 is obtained.e.12) What equation 1.11 gives the particularly useful expression 1.9) The equilibrium constant for this reaction is given by equation 1. NH2-. we will use it for a wide variety of acids and bases which are much too strong to exist in aqueous solution without reacting with the water. HB + A- (1. and that the equilibrium constant for the reaction will be given by the ratios of the Ka values for the two acids.12 can be rewritten as the useful equations 1.12. expression 1. then the equilibrium for the reaction of HA with B.
4-6 CH3CO³O NH2-. 33-38 (CH3)2CH³ NHCH3CO³ NH15-17 NH3. we must first identify the acid and the base.Table 1. we must keep in mind that there is one acid and . 45-60 [(CH2)5CH]CH3³CC25-30 CC³H RCC³H COC³ RCOCR2³ CH3COCH3 RCOCR2H H CH3COCH2. Functional Acidic Group alcohol Bond O³H Acid RO³H Examples H2O. H CH3CO³ OH N³H R2N³H RCO³O- HCO³O-. (CH3)3C³ O- pKa range 15-19 carboxylic acid amine COO³ RCOO³H HCO³OH. ketone CON³ RCONR³ H H C³H R³H CH4. While doing so.25-30 Let us now examine some examples of acid-base reactions in organic chemistry. (CH3)3C³ OH Conjugate Base ROExamples OH-. R2N(CH3)2CH³ NH2 CH3CO³ NH2 RCONR- amide alkane alkyne aldehyde. and see just how to approasch the problems associated with proton transfer chemistry. as in all potential acid-base reactions. CH3Li + H2O In this reaction. (CH2)6 RCH3³CC³ RCCH CH3-.8 Typical Ranges of pKa Values for Representative Acids. Example 1.
LiN(CH3)2. so we expect that methyllithium will react completely with water to give methane gas and lithium hydroxide. and we are usually safe in considering that such compounds will react as ionic compounds containing Li+ cations. From the data in Table 1.one base on each side of the arrow.8. CH3³H (or CH4). we find that the pKa of H2O is in the range 15-18. is to identify the acid and the base. (CH2)5. LiN(CH3)2 + (CH2)5 Our first step this reaction. This means that methyllithium also contains the CH3.will readily lose a proton to become CH22-. and the pKa of CH4 is in the range 45-60. H2O. Example 2. CH3Li. also. More importantly. Therefore. These are both huge numbers. it is the conjugate base of methane. we can fill out the table of reacting species: Reacting species Acid Base H2O CH3Conjugate OHCH4 This now allows us to write the balanced equation for this reaction: CH3. lithium.anion. In this example. and cyclopentane. we may consider that the lithium dimethylamide will react as an ionic lithium compound. we obtain: and as the minimum and maximum values for the equilibrium constant for this reaction. At this point. the two species reacting are lithium dimethylamide. This ion is capable of accepting a proton to become the neutral molecule. it is highly unlikely that CH3. On substituting these values in Equation 1. In this example.+Li + H2O CH4 + Li+ -OH. Again. methane. It does ³ methyllithium is rapidly (explosively) and quantitatively destroyed by water. . the water is almost certain to be the source of protons in this reaction. the two species reacting are methyllithium. and water. which means that it contains the (CH3)2Nanion.14. This ion is capable of accepting a proton to become the neutral molecule. The methyllithium is a compound that contains a Group IA metal.
8. the cyclopentane. we can fill out the table of reacting species: Reacting species Acid Base (CH2)5 (CH3)2NConjugate [(CH2)4CH](CH3)2NH This now allows us to write the balanced equation for this reaction: (CH3)2N.14. we find that the pKa of (CH2)5 is in the range 45-60. it is the conjugate base of dimethylamine.8. (CH3)2N³H.Li+. Sample Problem 1. At this point. Complete the following equations using the approximate pKa values given in Table 1. Therefore. (a) CH3CH2CH2CH2Li + CH3OH (b) NaNH2 + HCC³CH2CH3 (c) LiN(CH3)2 + (CH2)5 .dimethylamine. If no reaction should occur. From the data in Table 1. these numbers suggest that the reverse reaction (between cyclopentyllithium and dimethylamine to give cyclopentane and lithium dimethylamide) should be the one that actually occurs. and this is observed. and the pKa of (CH3)2NH is in the range 33-38. so we expect that lithium dimethylamide will not react with cyclopentane.+Li + (CH2)5 (CH3)2NH + [(CH2)4CH]. In fact. which cannot accept a proton. On substituting these values in Equation 1. These are both very small numbers.16. we obtain: and as the maximum and minimum values for the equilibrium constant for this reaction. write "N/R" and give the reason. is forced to be the source of protons in this reaction.
which is a stronger acid than (CH3)4C. but the boiling point of diethyl ether is 35°C while the boiling point of n-butyl alcohol is 118°C. we can calculate that the equilibrium constant in favor of products will be less than 10-5. making it a stronger acid than ammonia. CH3CH2C(CH3)2OH. Problem 1.16. Explain these observations. (CH3)3CCH2CH2OH. (c) (CH3)3CCH2NH2. n-Butyl alcohol (CH3CH2CH2CH2OH) and diethyl ether (CH3CH2OCH2CH3) have the same solubility in water. (CH3CH2)CHOH. only the hydrogen directly attached to the triple bond is attacked.15. (CH3CH2)3COH. (b) (CH3)3COH. (a) CH3(CH2)4OHCH3. The conjugate acid of LiN(CH2CH3)2 is H-N(CH2CH3)2. the equilibrium strongly favors the weaker acid and the weaker base.13 and the pKavalues in Table 1. (c) LiN(CH2CH3)2 + (CH3)4C N/R. . corresponding to no reaction. Its pKa from Table 1. (CH3)2NCH2CH2CH3. Problem 1. Give your reasoning. Using equation 1.8 is approximately 25-30. Arrange the following compounds in the expected increasing order of their solubility in water.Answers: (a) CH3CH2CH2CH2Li + CH3OH CH3CH2CH2CH3 + Li+OCH3(b) NaNH2 + HCC³CH2CH3 Na+ -CC³CH2CH3 + NH3 Note that in this reaction.8. (CH3)2CHCH2NHCH3. the approximate pKa values of the other hydrogens are predicted to be in the 45-60 range.
Leveling effect There is one very important consequence of equations 1. hydronium ion. and the stronger base will.13. methyllithium (CH3Li) in any solvent with a pKa less than this. we see that if one tries to use methyllithium in water. H3O+. For example. similar errors are frequently made using other incompatible acid-base combinations. because it reacts with the water to give the conjugate acid of water. Simply stated. above.because the stronger acid will simply react with the water to give hydronium ion. this means that any attempt to use an acid stronger than hydronium ion. the solvent limits both the strongest acid you can use (the conjugate acid of the solvent) and the strongest base (the conjugate base of the solvent). In water. react with the water to give hydroxide ion. one cannot use concentrated sulfuric acid (pKa = ³7) in aqueous solution. the solvent reacts with the base to give lithium hydroxide (the conjugate base of water) and methane. one cannot use its conjugate base. as is any attempt to use a base stronger than hydroxide ion. H3O+. these two react to give water. .in the same solution: of course. In other words.16(a).12 and 1. likewise. Using the equation of Sample Problem 1. and this is known as the leveling effect. for example. is doomed to failure. the leveling effect states that one cannot use an acid or base in a solvent which has a stronger conjugate base or acid than the acid one is trying to use. For similar reasons. since methane (CH4) has a pKa of 45-60. OH. It is a frequent and common error committed by learning students to attempt to use H3O+ and OH.
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