Acids and Bases

Brønsted-Lowry Acids and Bases ‡ A Brønsted-Lowry acid is a proton donor. ‡ A Brønsted-Lowry base is a proton acceptor. ‡ H+ = proton
Figure 2.1
Examples of Brønsted±Lowry acids and bases

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Some molecules contain both hydrogen atoms and lone pairs and thus, can act either as acids or bases, depending on the particular reaction. An example is the addictive pain reliever morphine.

2

Which of the following molecules is not a BromstedLowry acid? HBr NH3 CCl4

Bromsted-Lowry acid must contain a proton. Which of the following is not a Bromsted-Lowry base?
H3 C CH3 O

Bromsted-Lowry bases must have a lone pair or pi bond to donate.
3

4 . ‡ The electron pair of the base B: forms a new bond to the proton of the acid. one bond is broken. leaving the electron pair in the H²A bond on A.Reactions of Brønsted-Lowry Acids and Bases ‡ A Brønsted-Lowry acid base reaction results in the transfer of a proton from an acid to a base. ‡ In an acid-base reaction. and another one is formed. ‡ The acid H²A loses a proton.

These are equilibrium arrows. ‡ Loss of a proton from an acid forms its conjugate base. two curved arrows are needed. Examples: 5 .‡ The movement of electrons in reactions can be illustrated using curved arrow notation. ‡ Gain of a proton by a base forms its conjugate acid. ‡ A double reaction arrow is used between starting materials and products to indicate that the reaction can proceed in the forward and reverse directions. Because two electron pairs are involved in this reaction.

O O + H3C CH3 O CH3 H3C CH2 + HO CH3 A B CB CA Use curved arrows to show the movement of electron pairs. O O + H3C CH2 H O CH3 H3C CH2 + HO CH3 6 . conjugate acid and conjugate base in the following reaction.Label the acid. base.

Draw the products of the following reaction ( use curved arrows to show movement of electron pairs) H3C NH2 + HCl H3C NH2 + H Cl H3C NH3 + Cl H H + H H H + H H + H H 7 .

Acid Strength and pKa ‡ Acid strength is the tendency of an acid to donate a proton. ‡ The more readily a compound donates a proton. ‡ When a Brønsted-Lowry acid H²A is dissolved in water. the stronger an acid it is. an acid-base reaction occurs. and an equilibrium constant can be written for the reaction. 8 . ‡ Acidity is measured by an equilibrium constant.

It is generally more convenient when describing acid strength to use ³pKa´ values than Ka values. 9 .Because the concentration of the solvent H2O is essentially constant. called the acidity constant. can be defined. the equation can be rearranged and a new equilibrium constant. Ka.

10 .

the same procedure is always followed. o The more stable the conjugate base.Factors that Determine Acid Strength ‡ ‡ Anything that stabilizes a conjugate base A:¯ makes the starting acid H²A more acidic. the more acidic the acid. These are: Element effects Inductive effects Resonance effects Hybridization effects ‡ No matter which factor is discussed. 11 . o Determine which conjugate base is more stable. To compare the acidity of any two acids: o Always draw the conjugate bases. Four factors affect the acidity of H²A.

Element Effects²Trends in the Periodic Table. the acidity of H²A increases as the electronegativity of A increases. 12 . Positive or negative charge is stabilized when it is spread over a larger volume. Across a row of the periodic table.

the acidity of H²A increases as the size of A increases. ‡ The acidity of H²A increases both left-to-right across a row and down a column of the periodic table. determines acidity down a column. ‡ Size. element effects²the identity of A²is the single most important factor in determining the acidity of the H²A bond. 13 . ‡ Although four factors determine the overall acidity of a particular hydrogen atom. and not electronegativity.‡ Down a column of the periodic table.

2. we note that the latter is more acidic than the former. 14 . ‡ In the example below. when we compare the acidities of ethanol and 2.Factors that Determine Acid Strength²Inductive Effects ‡ An inductive effect is the pull of electron density through W bonds caused by electronegativity differences between atoms.2-trifluoroethanol.

2.2trifluoroethanol is that the three electronegative fluorine atoms stabilize the negatively charged conjugate base. 15 .‡ The reason for the increased acidity of 2.

16 . ‡ More electronegative atoms stabilize regions of high electron density by an electron withdrawing inductive effect. the greater the effect.‡ When electron density is pulled away from the negative charge through W bonds by very electronegative atoms. ‡ The acidity of H²A increases with the presence of electron withdrawing groups in A. it is referred to as an electron withdrawing inductive effect. ‡ The more electronegative the atom and the closer it is to the site of the negative charge.

17 . ‡ In the example below. when we compare the acidities of ethanol and acetic acid. we note that the latter is more acidic than the former. it is evident that the conjugate base of acetic acid enjoys resonance stabilization.Factors that Determine Acid Strength²Resonance Effects ‡ Resonance is a third factor that influences acidity. ‡ When the conjugate bases of the two species are compared. whereas that of ethanol does not.

‡ The acidity of H²A increases when the conjugate base A:¯ is resonance stabilized. so CH3COOH is a stronger acid than CH3CH2OH. 18 .‡ Resonance delocalization makes CH3COO¯ more stable than CH3CH2O¯.

‡ Electrostatic potential plots of CH3CH2O¯ and CH3COO¯ below indicate that the negative charge is concentrated on a single O in CH3CH2O¯. but delocalized over both of the O atoms in CH3COO¯. 19 .

and the more stable the conjugate base. ‡ The higher the percent of s-character of the hybrid orbital. the closer the lone pair is held to the nucleus. Let us consider the relative acidities of three different compounds containing C²H bonds.Factors that Determine Acid Strength²Hybridization Effects ‡ The final factor affecting the acidity of H²A is the hybridization of A. 20 .

21 .

5 Summary of the factors that determine acidity 22 .Figure 2.

Calculate the pka¶s and which is the stronger acid? OH CH3 ka= pka= 10-10 10 10-41 41 OH 23 .

7 24 .7) CH4 (pka= 58) CH4 Draw the products and determine the direction of the equilibrium.Which is the strongest base? H20 (pka= 15. CH4 + OH NH3 (pka= 38) CH3 + H2 O pka= 50 15.

b/c Br is further to the right and further down in the periodic table. which is the stronger acid? H 2S HBr HBr.8) ? l pka= 25 35 -7 Both acetylene and hydrogen will work (must have higher pka) Not using pka.Which of these bases is strong enough to deprotonate CH3COOH (pka= 4. 25 .

Which is the stronger acid? F2CHCH2COOH OR Cl2CH2COOH F2CHCH2COOH is the most acidic b/c acids are stabilized by electron withdrawing groups and F is more electronegative than Cl Which is the stronger acid and why? H H H B/c the C-H bond involves sp2 hybridized orbital instead of sp3 26 .

Two examples are acetic acid and p-toluenesulfonic acid (TsOH). a number of other acids are often used in organic reactions. 27 . H2SO4 and HNO3.Commonly Used Acids in Organic Chemistry In addition to the familiar acids HCl.

28 .Commonly Used Bases in Organic Chemistry Common strong bases used in organic reactions are more varied in structure.

but not all negatively charged species are strong bases. are especially strong bases.It should be noted that: ‡ Strong bases have weak conjugate acids with high pKa values. 29 . is a strong base. negatively charged carbon atoms. or I¯. ‡ Strong bases have a net negative charge. Br¯. ‡ Carbanions. ‡ Two other weaker organic bases are triethylamine and pyridine. none of the halides F¯. usually > 12. For example. A common example is butyllithium. Cl¯.

‡ A Lewis base is an electron pair donor. 30 .Lewis Acids and Bases ‡ The Lewis definition of acids and bases is more general than the BrØnsted-Lowry definition. ‡ Lewis bases are structurally the same as BrØnsted-Lowry bases. ‡ A BrØnsted-Lowry base always donates this electron pair to a proton. Both have an available electron pair²a lone pair or an electron pair in a T bond. but a Lewis base donates this electron pair to anything that is electron deficient. ‡ A Lewis acid is an electron pair acceptor.

o Any species that is electron deficient and capable of accepting an electron pair is also a Lewis acid. ‡ All BrØnsted-Lowry acids are also Lewis acids. ‡ Common examples of Lewis acids (which are not BrØnstedLowry acids) include BF3 and AlCl3. but the reverse is not necessarily true.‡ A Lewis acid must be able to accept an electron pair. 31 . but there are many ways for this to occur. These compounds contain elements in group 3A of the periodic table that can accept an electron pair because they do not have filled valence shells of electrons.

‡ Lewis acid-base reactions illustrate a general pattern in organic chemistry. 32 . ‡ In a Lewis acid-base reaction. This is illustrated in the reaction of BF3 with H2O.‡ Any reaction in which one species donates an electron pair to another species is a Lewis acid-base reaction. ‡ In the simplest Lewis acid-base reaction one bond is formed and no bonds are broken. H2O donates an electron pair to BF3 to form a new bond. a Lewis base donates an electron pair to a Lewis acid. Electron-rich species react with electronpoor species.

In this example. BF3 is the electrophile and H2O is the nucleophile. the Lewis base is also called a nucleophile. electrophile nucleophile 33 .‡ A Lewis acid is also called an electrophile. ‡ When a Lewis base reacts with an electrophile other than a proton.

it is donated to an atom of the Lewis acid and one new covalent bond is formed. Note that in each reaction. 34 . the electron pair is not removed from the Lewis base. Instead.‡ Two other examples are shown below.

To draw the products of these reactions. Count electron pairs and break a bond when needed to keep the correct number of valence electrons. 35 . Draw a curved arrow from the electron pair of the base to the electron-deficient atom of the acid.‡ In some Lewis acid-base reactions. one bond is formed and one bond is broken. keep in mind the following steps: Always identify the Lewis acid and base first.

and cyclohexene.Consider the Lewis acid-base reaction between cyclohexene and H²Cl. The BrØnsted-Lowry acid HCl is also a Lewis acid. 36 . is the Lewis base. having aT bond.

‡ To draw the product of this reaction. 37 . forming Cl¯. ‡ The H²Cl bond must break. ‡ Because two electron pairs are involved. giving its two electrons to Cl. two curved arrows are needed. generating a carbocation. the electron pair in the T bond of the Lewis base forms a new bond to the proton of the Lewis acid.

Which is not a Lewis acid? Br OH B Br Br CH None. all are Lewis acids b/c they either contain an unfilled valence shell or an acidic proton. 38 .Which is not a Lewis base? NH3 Lewis base must have an electron pair to donate.

39 .

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