Acid-base reactions protons

Proton transfer is a particularly important transport process. Beyond acid-base reactions, proton transfer may be coupled to electron transfer in redox reactions and to excited-state chemistry. It is of enormous significance in biochemical processes where it is an essential step in hydrolytic enzyme processes and redox reactions spanning respiration, and photosynthesis where proton motion is responsible for sustaining redox gradients. In relatively recent times, proton transfer in the excited state has undergone significant study, primarily fueled by advances in ultrafast spectroscopy. 

The donor-acceptor principle is an important basic concept in modern chemical education acid-base reactions, redox reactions and complex reactions explain a huge number of chemical changes. One important group of donor-acceptor reactions are the acid-base reactions protons (H+ ions) transfer from one species to another species. One example, in the neutralization of sulfuric acid with sodium hydroxide a proton is moving from one hydronium ion H30 + (aq) of the acid solution to one hydroxide ion OH (aq) ion of the hydroxide solution. Broensted s key concept will be considered in this chapter. 

Note that Bronsted-Lowry acid-base reactions (proton donor-proton acceptor reactions) are encompassed by the Lewis model. For example, the reaction between a proton and an ammonia molecule, that is. 

STEP 1 Add a proton. An acid-base reaction protonates the /3-hydroxyl group. 

Another solvent that may be used for acid-base reactions (proton transfer) is concentrated sulfuric acid. This is both an acid and a solvent for the nitration of benzene. 

In a Bronsted-Lowry acid-base reaction, protons are transferred from one reactant (the acid) to another (the base). Figure 2.1 shows the reaction between the Bronsted-Lowry acid HCl and the Bronsted-Lowry base NH3. 

A polyprotic acid is capable of losing more than a single proton per molecule in acid-base reactions. Protons are lost in a stepwise fashion, with the first proton being the most readily lost. 

The Lewis definitions of acids and bases provide for a more general view of acid-base reactions than either the Arrhenius or Br0nsted-Lowry pic ture A Lewis acid is an electron pair acceptor A Lewis base is an electron pair donor The Lewis approach incorporates the Br0nsted-Lowry approach as a subcategory m which the atom that accepts the electron pair m the Lewis acid is a proton... 

The first step of this new mechanism is exactly the same as that seen earlier for the reaction of tert butyl alcohol with hydrogen chloride—formation of an alkyloxonmm ion by proton transfer from the hydrogen halide to the alcohol Like the earlier exam pie this IS a rapid reversible Brpnsted acid-base reaction... 

Step 3 This step is a fast acid base reaction that follows the nucleophilic substitution Water acts as a base to remove a proton from the alkyloxonium ion to give the observed product of the reaction tert butyl alcohol... 

Acetylenic Grignard reagents of the type RC CMgBr are prepared not from an acetylenic halide but by an acid-base reaction in which a Grignard reagent abstracts a proton from a terminal aUcyne... 

The acid-base reactions that occur after the amide bond is broken make the overall hydrolysis irreversible m both cases The amine product is protonated m acid the car boxylic acid is deprotonated m base... 

In an acid-base reaction, the reaction unit is the proton. For an acid, the number of reaction units is given by the number of protons that can be donated to the base and for a base, the number of reaction units is the number of protons that the base can accept from the acid. In the reaction between H3PO4 and NaOH, for example, the weak acid H3PO4 can donate all three of its protons to NaOH, whereas the strong base NaOH can accept one proton. Thus, we write... 

Acid-base reactions occur when an acid donates a proton to a base. The equilibrium position of an acid-base reaction is described using either the dissociation constant for the acid, fQ, or the dissociation constant for the base, K, . The product of and Kb for an acid and its conjugate base is K (water s dissociation constant). 

Quantitative Calculations In acid-base titrimetry the quantitative relationship between the analyte and the titrant is determined by the stoichiometry of the relevant reactions. As outlined in Section 2C, stoichiometric calculations may be simplified by focusing on appropriate conservation principles. In an acid-base reaction the number of protons transferred between the acid and base is conserved thus... 

Step 3 is new to us. It is an acid-base reaction in which the carbocation acts as a Br0n-sted acid, transferiing a proton to a Brpnsted base (water). This is the property of carbocations that is of the most significance to elimination reactions. Car bocations ar e strong acids they are the conjugate acids of alkenes and readily lose a proton to form alkenes. Even weak bases such as water are sufficiently basic to abstract a proton from a carbocation. 

Whenever possible, the chemical reactions involved in the fonnation of diastereomers and their- conversion to separate enantiomers are simple acid-base reactions. For example, naturally occurring (5)-(—)-malic acid is often used to resolve fflnines. One such amine that has been resolved in this way is 1-phenylethylarnine. Amines are bases, and malic acid is an acid. Proton transfer from (5)-(—)-malic acid to a racemic mixture of (/ )- and (5)-1-phenylethylarnine gives a mixture of diastereorneric salts. 

As pointed out in Chapter 4, the first step in the reaction is proton transfer to the alcohol from the hydrogen halide to yield an alkyloxonium ion. This is an acid-base reaction. 

Table 4-1 lists some rate constants for acid-base reactions. A very simple yet powerful generalization can be made For normal acids, proton transfer in the thermodynamically favored direction is diffusion controlled. Normal acids are predominantly oxygen and nitrogen acids carbon acids do not fit this pattern. The thermodynamicEilly favored direction is that in which the conventionally written equilibrium constant is greater than unity this is readily established from the pK of the conjugate acid. Approximate values of rate constants in both directions can thus be estimated by assuming a typical diffusion-limited value in the favored direction (most reasonably by inspection of experimental results for closely related... 

Hydrogen peroxide has a rich and varied chemistry which arises from (i) its ability to act either as an oxidizing or a reducing agent in both acid and alkaline solution, (ii) its ability to undergo proton acid/base reactions to form... 

Acid-base reactions in anhydrous HF are well documented. Within the Brpnsted formalism, few if any acids would be expected to be sufficiently strong proton donors to be able to protonate the very strong proton-donor HF (p. 51), and this is borne out by observation. Conversely, HF can protonate many Brpnsted bases, notably water. 

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