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Chapter 15. Acids and Bases. Acids & Bases. These were introduced in Chapter 4 Arrhenius: Acid = any substance that produces H + in soution . Base = any substance that produces OH - in solution. Bronsted -Lowery Theory.
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Chapter 15 Acids and Bases
Acids & Bases • These were introduced in Chapter 4 • Arrhenius: • Acid = any substance that produces H+ in soution. • Base = any substance that produces OH- in solution.
Bronsted-Lowery Theory • Definition of acids and bases focused on the transfer of a single proton. • Acid = any substance that donates a proton (H+). • Base = any substance that accepts a proton (H+). • Expands the number of acids and bases. • Not restricted to aqueous solutions.
Hydronium Ion • In water, HCl dissociates completely to: HCl(aq) H+(aq) + Cl-(aq) • In essence, this shows that a free proton is present. • In reality, this does not ever happen! HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)
Bronsted-Lowery Theory • As mentioned, acid-base reactions do not have to be aqueous. NH3(g) + HCl(aq) NH4+(s) + Cl-(s)
Acid-Base Equilibrium • In any acid-base equilibrium reaction, both the forward and the reverse reactions involve the transfer of a proton. NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) HF(aq) + H2O(l) H3O+(aq) + OH-(aq)
Acid-Base Equilibrium • Any two substances on either side of the double arrow that differ by a proton are called a conjugate acid-base pair. • Thus, every acid has a conjugate base made by removing the proton and every base has a conjugate acid made by adding a proton. • What did you notice about the role of water in the previous two reactions?
Strong Acids • Strong acids completely ionize, leaving no un-dissociated molecules in solution. • Only six acids are considered “strong.” • The conjugate base of a strong acid has no base properties. • Acid strengths sheet shows the order of strengths. • Weaker the acid, the stronger the conjugate base. • HCl(aq) + H2O(aq) H3O+(aq) + OH-(aq)
Strong Bases • Strong Bases completely ionize, due to the fact that they are ionic. • Only the group 1A and 2A metal hydroxides are considered to be “strong”. • All other hydroxides are insoluble in water. • NaOH(aq) Na+(aq) + OH-(aq)
Auto-Ionization of Water • On rare occasion, two water molecules react with each other.
Auto-Ionization of Water • Because water is a liquid, this is a heterogeneous equilibrium. • Kw= • At 25oC, the value of Kw = 1.0 E-14. • This is called the ion-product constant. • Allows us to calculate an unknown [H3O+] or [OH-].
pH Scale • Uses a logarithm in base 10, which is different than the natural logarithm. • The letter “p” always represents the negative logarithm in chemistry. • pH = -log[H+] • pOH = -log[OH-] • pH + pOH = 14
pH Scale • A word about significant figures. • Suppose that the [H3O+] = 2.4 x 10-3 M • pH = -log(2.4 E-3) = 2.619788… • 2.4 x 10-3M pH = 2.62 • Red numbers are the significant digits. • Blue numbers are exact numbers.
Acidic or Basic? • When the [H3O+] > [OH-], the solution is acidic. • When the [OH-] > [H3O+], the solution is basic. • What about pH?
pH of Strong Acids and Bases • Since these dissociate 100%, these are relatively easy. • 0.10M HCl would produce ____M H3O+ • 0.025M NaOH would produce ____M OH- • 0.030M Ca(OH)2 would produce ____M OH- • Can also have gram and volume amounts. • Can also do partial neutralization.
Weak Acids • A weak acid only partially ionizes. • Too many to list, but formula generally begins with an “H”. • Appendix D1 lists many weak acids. • Equilibrium constant is called Ka. • Will require an ICE table to find the pH.
Weak Acids • General set-up is: • HA + H2O H3O+ + A- I C E • Appendix D1 used to find the Ka values. • Problem will look like a quadratic problem, but …
Weak Acids • Problems may include: • Finding a pH from starting concentration. • Finding a Ka value given pH and starting concentration. • Finding a percent ionization.
Polyprotic Acids • A polyprotic acid contains two or more acidic protons per molecule. • Some common ones include: H3PO4 and H2CO3. • One is also a strong acid: H2SO4. • All ionize in successive steps and have multiple Ka values. • Intuitively, each H+ is more and more difficult to remove.
Weak Bases • A weak base reacts with water, which donates a proton to the N atom. • N atom has lone pair to bond the proton. • Table D2 lists some examples of the weak bases. • The equilibrium constant is called Kb. • Will require an ICE table for most problems.
Weak Bases • Generally, the set-up is: B + H2O BH+ + OH- I C E • Appendix D2 has Kb values. • Will look like a quadratic, but…
Weak Bases • Problems may include: • Finding a pH from starting concentration. • Finding a Ka value given pH and starting concentration. • Finding a percent ionization.
Conjugate Pairs • NH3 is a base and NH4+ is its conjugate acid. NH3 + H2O NH4+ + OH- Kb = 1.8 x 10-5 NH4+ + H2O H3O+ + NH3 Ka = ??? • What if we need the Ka for NH4+?
Conjugate Pairs • Like a pH = -log[H+], there is also a pKa and a pKb. • For any conjugate pair, the pKa + pKb = __. • Can also convert a pKa back to a Ka.
Salts • Solutions of NaF are always basic and solutions of NH4Cl are always acidic. • On the other hand, a solution of NaCl is neutral. • Why??? • Predicting and calculating a pH of various salts based on the hydrolysis of certain ions.
Salts • Salts containing the cation of a _________ and an anion of a _________ will be neutral. • Salts containing the cation of a _________ and an anion of a _________ will be __________. • Salts containing the cation of a _________ and an anion of a __________ will be _________. • Salts containing the cation of a _________ and an anion of a _________ can be ____________. • Transition metal and Al ions of high charge will be ____________.
Structure and Strength • Acid strength can be predicted based on two factors. • Factor #1: Degree of polarity of the H-X bond. This depends on E.N. difference. • Rule: • Factor #2: Bond Strength • Ch. 8: HI = 299kJ, HBr = 366kJ, HCl = 431kJ, and HF = 567kJ • Rule:
Structure and Strength • Binary Acids – hydrogen is bonded to only one other element. • Bond strength (factor #2) is most important. • Which group 7A acid is the strongest? Weakest? • General Rule =
Structure and Strength • Oxy-acids are very common. • General structure is: H – O – X • For all of these, factor #1 is dominant. • For oxy-acids where the number of oxygen atoms differs and X is the same. • For oxy-acids where the number of oxygen atoms are identical, but the X atom varies.
Structure and Strength • Carboxylic acids are organic acids containing the –COOH group. • Acidic due to stability of –COO- group. • Increasing strength by adding electronegative atoms. • CH3COOH vs. CF3COOH