Chapter 8 Acid-Base Equilibria 8-1 Brønsted-Lowry Acids and Bases 8-2 Water and the ph Scale 8-3 The Strengths of Acids and Bases 8-4 Equilibria Involving Weak Acids and Bases 8-5 Buffer Solutions 8-6 Acid-Base Titration Curves 8-7 Polyprotic Acids 8-8 Lewis Acids and Bases 2/6/2004 OFB Chapter 8 1
Acid and Base Definitions 1) Arrhenius (Section 4.3) Acids are H donors Bases are OH - donors 2) Broadened Definition (Section 4.3) Acids are substances that increase [H ] Bases are substances that increase [OH - ] 3) Brønsted-Lowry (Section 8.1) 4) Lewis (Section 8.8) 2/6/2004 OFB Chapter 8 2
Chapter 8 Acid-Base Equilibria Brønsted-Lowry Acids Bases Conjugate Base - Conjugate Acid 2/6/2004 OFB Chapter 8 3
Acid-Base Equilibria Brønsted-Lowry Acids and Bases A Brønsted-Lowry acid is a substance that can donate a hydrogen ion. A Brønsted-Lowry base is a substance that can accept a hydrogen ion. In the Brønsted-Lowry Acid and Base concept, acids and bases occur as conjugate acid-base pairs. 2/6/2004 OFB Chapter 8 4
Conjugate Base - subtract an H from the acid Conjugate Acid add H to the base Examples 1. is the conjugate base of H 2 O 2. is the conjugated base of H 3 O (called the hydronium ion) 3. is the conjugated acid of OH - 4. (or shown as H) is the conjugate acid of H 2 O 2/6/2004 OFB Chapter 8 5
Conjugate Base - subtract an H from the acid Conjugate Acid add H to the base H 2 O -H H Hydroxide ion conjugate OH - base of H 2 O conjugate acid of H 2 O H 3 O Hydronium ion H -H Water is the conjugate acid of OH - H 2 O Water is the conjugate base of H 3 O 2/6/2004 OFB Chapter 8 6
CH 3 CO 2 H H 2 O H 3 O CH 3 CO 2 - Acetic Acid Acetate Ion Pairs 1 2 2 1 acid base acid base Point of View #1 CH 3 CO 2 H H 2 O H 3 O CH 3 CO 2 - acid base Conjugate acid of H 2 O Conjugate base of CH 3 CO 2 H Point of View #2 CH 3 CO 2 H H 2 O H 3 O CH 3 CO 2 - Conjugate acid of CH 3 CO 2 - Conjugate base of H 3 O acid base 2/6/2004 OFB Chapter 8 7
Autoionization of H 2 O H 2 O H 2 O H 3 O OH - Pairs 1 2 2 1 acid base acid base Point of View #1 H 2 O H 2 O H 3 O OH - # 1 # 2 acid base Conjugate acid of H 2 O #2 Conjugate base of H 2 O #1 Point of View #2 H 2 O H 2 O H 3 O OH - Conjugate acid of OH - Conjugate base of H 3 O acid base 2/6/2004 OFB Chapter 8 8
Exercise 8-1: Trimethylamine (C 3 H 9 N) is a soluble weak base with a foul odor (it contributes to the smell of rotten fish). Write the formula of its conjugate acid. the formula of a conjugate acid is obtained by adding H to the formula of the base. 2/6/2004 OFB Chapter 8 9
Nomenclature When H is hydrated it is H 3 O and called a hydronium ion. Often H 3 O is written in a simpler notation H 111.7 2/6/2004 OFB Chapter 8 10
Amphoterism - an ion or molecule can act as an acid or base depending upon the reaction conditions 1.) Water in NH 3 serves as an acid H 2 O NH 3 NH 4 OH - 2.) Water in acetic acid serves as a base H 2 O CH 3 CO 2 H H 3 O CH 3 CO 2-2/6/2004 OFB Chapter 8 11
3.) Acetic Acid is also amphoteric, if in the presence of a strong acid serves as a base H 2 SO 4 CH 3 CO 2 H CH 3 CO 2 H 2 HSO4 - Amphoterism - an ion or molecule can act as an acid or base depending upon the reaction conditions 2/6/2004 OFB Chapter 8 12
Water Autoionization of water: 2 H 2 O(l) H 3 O (aq) OH - (aq) [H 3 O ][OH - ] [H 2 O] 2 K W 1.0 10-14 (at 25 o C) 2/6/2004 OFB Chapter 8 13
Strong Acids and Bases A strong acid is one that reacts essentially completely with water to produce H 3 O (aq). Hydrochloric acid (HCl) is a strong acid: HCl (aq) H 2 O(l) H 3 O (aq) Cl - (aq) (reaction essentially complete) Dissolving 0.10 mol of HCl in enough water to make 1.0 L of solution gives a final concentration of 0.10 M for H 3 O (aq). [H 3 O ][OH - ] K W 2/6/2004 OFB Chapter 8 14
A strong base is one that reacts Strong Acids and Bases essentially completely with water to produce OH - (aq) ions. Sodium hydroxide (NaOH) is a strong base: Others are NH 2- (amide ion) and H - (Hydride ion) NaOH(s) Na (aq) OH - (aq) (reaction essentially complete) Dissolving 0.10 mol of NaOH in enough water to make 1.0 L of solution gives a final concentration of 0.10 M for OH - (aq). [H 3 O ][OH - ] K W 2/6/2004 OFB Chapter 8 15
ph -log 10 [H 3 O ] The ph Function ph < 7 acidic solution [H 3 O ] > [OH - ] ph 7 neutral solution [H 3 O ] [OH - ] ph > 7 basic solution [H 3 O ] < [OH - ] 2/6/2004 OFB Chapter 8 16
The ph Function EXAMPLE 8-3 Calculate the ph (at 25 o C) of an aqueous solution that has an OH - (aq) concentration of 1.2 10-6 M. 2/6/2004 OFB Chapter 8 17
ph -log 10 [H 3 O ] If converting from ph to [H ] [H ] 10 -ph 10 -X 2/6/2004 OFB Chapter 8 18
Recall [H 3 O ][OH - ] K W 10-14 ph poh pk w 14 2/6/2004 OFB Chapter 8 19
The ph Function Exercise page 8-4: Calculate [H 3 O ] and [OH - ] in saliva that has a ph of 6.60 at 25 o C. 2/6/2004 OFB Chapter 8 20
Strengths of Acids and Bases Strong acids (completely ionized in water, i.e., 100%) 1. HI 2. HBr 3. HClO4 (perchloric acid) 4. HCl 5. HClO3 (chloric acid) 6. H2SO4 7. HNO3 HA H 2 O H 3 O A HA generic acid K a [H3O ][A ] [HA][H O] 2 [H3O ][A [HA] ] 2/6/2004 OFB Chapter 8 21
pk log a 10 K a Table 8-2 Scale of pka -11 To 14 Known Scale of pka -11 To 50 E.g., Acetone 19, methane 48, ethane 50 2/6/2004 OFB Chapter 8 22
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Strengths of Acids and Bases B H 2 O BH OH - B Base K b [BH ][OH [B][H O] [BH 2 ][OH [B] ] ] pk log b 10 K b K b is the Basicity constant 2/6/2004 OFB Chapter 8 24
B H 2 O BH OH - B Base K b [BH ][OH [B][H O] 2 ] pk log b 10 K b [BH ][OH [B] ] K b is the Basicity constant K a BH H 2 O B H 3 O B Base [B][H O [BH [B][H O [BH 3 ][H O] 3 ] 2 ] ] pk log 2/6/2004 OFB Chapter 8 25 a K a is the Acidity constant 10 K a
K b B H 2 O BH OH - B Base BH H 2 O B H 3 O B Base [BH ][OH [B][H O] [BH ][OH ] [B] [B][H3O KaKb [BH ] K 2 [H 3 w O ] K [B][H3O [BH ] [B][H O [BH ][H O] [B][H3O ] [BH ] ] [BH ][OH [B] 2/6/2004 OFB Chapter 8 26 a ][OH ] [BH ] 3 2 ][OH [B] ] ] ]
Chapter 8 Acid-Base Equilibria Base Strength strong acids have weak conjugate bases weak acids have strong conjugate bases The strength of a base is inversely related to the strength of its conjugate acid; the weaker the acid, the stronger its conjugate base, and vice versa K K a b K w pk a pk b pk w 2/6/2004 OFB Chapter 8 27
Indicators (denoted by In) A soluble compound, generally an organic dye, that changes its color noticeably over a fairly short range of ph. Typically, a weak organic acid that has a different color than its conjugate base. HIn(aq) H 2 O(l) H 3 O (aq) In - (aq) [H 3 O ][In - ] [HIn] K a 2/6/2004 OFB Chapter 8 28
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Methyl Red Bromothymol blue Phenolphtalein 2/6/2004 OFB Chapter 8 30
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Equilibria Involving Weak Acids and Bases Weak acids K a < 1 i.e., pk a > 0 H 3 O (hydronium ion) Ka 1 pka 0 HA H 2 O H 3 O A - HA is a weak acid, K a < 1 or pk a > 1 2/6/2004 OFB Chapter 8 32
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Problem: (a) Calculate ph and (b) the fraction of CH 3 CO 2 H ionized at equilibrium. Assume 1.0M CH 3 CO 2 H initially CH 3 CO 2 H H 2 O H 3 O CH 3 CO 2 - Init. conc. conc. Equil. conc. K a [H 3 [CH O 3 ][CH CO CO 2 3 H][H 2-2 ] O] 2/6/2004 OFB Chapter 8 35
K a [H 3 [CH O 3 ][CH CO CO 2 3 H][H 2-2 ] O] y 2 (1.0 y) K a 1.8x10 5 from Table 8-2 A trick to solving: Assume that y is small (less than 5% of the initial conc.) y 2 1.8x10 5 y ph 4.24 x 10-3 [H O - log (4.24x10 2.37 2/6/2004 OFB Chapter 8 36 3-3 ) ]
Problem: (a) Calculate ph and (b) the fraction of CH 3 CO 2 H ionized at equilibrium. Assume 1.0M CH 3 CO 2 H initially CH 3 CO 2 H H 2 O H 3 O CH 3 CO 2 - (b) Fraction CH 3 CO 2 H ionized at equilibrium 2/6/2004 OFB Chapter 8 37
Weak Bases Similarly NH 3 acts as a weak base in H 2 O K b 1.8 x 10-5 H 2 0 NH 3 NH 4 OH - acid 1 base 2 acid 2 base 1 K b [NH [NH 4 ][OH ] 1 3 ][H 2 - O] 2/6/2004 OFB Chapter 8 38
As before, you can calculate a ph at equilibrium. Assume 0.01M NH 3 initially. Calculate the ph of the resulting solution Init. conc. conc. H 2 0 NH 3 NH 4 OH - Equil. conc. K K b b for NH 4 [NH ][OH [NH ][1] 3 3-1.8x10 ] y2 (0.01 5 y) 2/6/2004 OFB Chapter 8 39
As before, you can calculate a ph at equilibrium. Assume 0.01M NH 3 initially. Calculate the ph of the resulting solution K K y b b - 2 4 [NH ][OH ] [NH ][1] 3 y 0.01 [OH ] [NH - 1.8x10 4 ] 5 2 y 0.01 y 4.2x10-4 H 3 O ph ] - log Kw [OH 10 ] (2.4x10 1x10 4.2x10-11 14 4 ) 10.62 2.4x10 11 2/6/2004 OFB Chapter 8 40
Hydrolysis is a term applied to reactions of aquated ions that change the ph from 7 When NaCl is placed in water, the resulting solution is observed to be neutral (ph 7) However when sodium acetate (NaC 2 H 3 O 2 ) is dissolved in water the resulting solution is basic Other salts behave similarly, NH 4 Cl and AlCl 3 give acid solutions. These interactions between salts and water are called hydrolysis 2/6/2004 OFB Chapter 8 41
Despite the special term, hydrolysis, there is no reason to treat hydrolysis in a special manner. It is still a Brønsted-Lowry Acid and Base Reaction 2/6/2004 OFB Chapter 8 42
Example problem: Suppose a 0.1 mole solution sodium acetate is dissolved in 1 liter of water. What is the ph of the solution? Init. conc. conc. Equil. conc. 1.Find K b 2.Find [OH - ] 3.Find [H ] 4.Find ph 2/6/2004 OFB Chapter 8 43
Example problem: What is the ph of the solution? CH 3 CO 2- H 2 O CH 3 CO 2 H OH - Init. conc. 0.1M 0 ~0 conc. - y y y Equil. conc. 0.1 y y y 1. Find K b 2. Find [OH - ] 3. Find [H ] 4. Find ph [H O 3 K K b b K K w a y [OH [CH CO 3 [CH CO K a x K b K w ] 2/6/2004 OFB Chapter 8 44 ph ] - log Kw [OH 10 ] (1.39x10 3-2H][OH ] - 2 ][1] 14 1.0x10 5 1.8x10 table 7.5x10 1x10 7.5x10-9 14 6 6 ) 8.89 1.3x10 2 y 0.1 y 5.6x10 9 4
Hydrolysis of Anions Result Raise ph Cations Lower ph Non-Hyrolyzed Ions (a few) 7 Anions, not hydrolyzed Cl -, Br -, I -, HSO 4-, NO 3-, ClO 3-, ClO 4-10 Cations, not hydrolyzed Li, Na, K, Rb, Sc, Mg, Ca, Sr, Ba, Ag 2/6/2004 OFB Chapter 8 45
Hydrolysis of Anions Result Raise ph Cations Lower ph Can predict ph of some salts (relative ph) Na 3 PO 4 is basic (a non hydrolyzed cation and a hydrolyzed anion) FeCl 3 is acidic (a hydrolyzed cation and a non hydrolyzed anion) 2/6/2004 OFB Chapter 8 46
Chapter 8 Acid-Base Equilibria Buffer Solutions: important in biochemical and physiological processes Organisms (and humans) have built-in buffers to protect them against large changes in ph. Buffers any solutions that maintain an approximately constant ph despite small additions of acids or bases 2/6/2004 OFB Chapter 8 47
Buffers any solutions that maintain an approximately constant ph despite small additions of acids or bases Human blood (ph7.4) is maintained by a combination of CO 3-2, PO 4-3 and protein buffers, which accept H Death 7.0 < ph > 7.8 Death How Do Buffers Work? 2/6/2004 OFB Chapter 8 48
How Do Buffers Work? HA H 2 O H 3 O A HA generic acid rearranged K [H 3 O ] [H 3 Ka K a O ][A [HA] a [HA] [A formula [H ] depends on K a and the ratio of acid to salt. Thus if both conc. HA and A - are large then small addictions of acid or base don t change the ratio much 2/6/2004 OFB Chapter 8 49 ] ]
HA H 2 O H 3 O A H depends on K a and the ratio of acid to salt. Thus if both conc. HA and A - are large then small addictions of acid or base don t change the ratio much Try Example 8-11 2/6/2004 OFB Chapter 8 50
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8-8 Lewis Acids Extremely important for Organic Chemistry Recall from Chapter 3 that main group elements in a molecule are surrounded by 8 electrons (the Octet Rule). Hydrogen by 2 electrons Carbon is 6 C or 1s 2 2s 2 2p 2 Hydrogen is 1 H or 1s 1 2/6/2004 OFB Chapter 8 53
Lewis Structures H H C H H H H C H Covalent bonds H CH 4 methane 2/6/2004 OFB Chapter 8 54
H N H H Lewis Structures Lone pair H N H H NH 3 ammonia H O H H O H H O water H 2/6/2004 OFB Chapter 8 55
Lewis Structures Electron deficient F F B F F B F F boron triflouride 2/6/2004 OFB Chapter 8 56
Chapter 8 Acid-Base Equilibria Lewis Acids-Bases Lewis Acid is any species that accepts electron pairs Called electrophiles (electron seeking) e.g., Boron, Al, Group III elements BF 3, Mg 2, H, H 3 O BH 3, SnCl 4, CH 3, AlCl 3, HCl 2/6/2004 OFB Chapter 8 57
Chapter 8 Acid-Base Equilibria Lewis Acids-Bases Lewis Base is any species that donates electrons through coordination to its lone pair Called Nucleophiles (nucleus seeking) e.g., Group V, VI, VII elements Br -1, Cl -1, F -1, H -1, HO -1, :NH 3, H 2 O:: O R N R O H R R R R Carbonyls Amines Alcohols 2/6/2004 OFB Chapter 8 58
H O H OH HOH HO H H Lewis Acid Lewis Base O O O H :NH 3 O - NH 4 H 3 C H 3 C acetic acid ammonia acetate ion ammonium ion Lewis Acid Lewis Base Lewis Base Lewis Acid 2/6/2004 OFB Chapter 8 59
Chapter 8 Acid-Base Equilibria Examples/Exercises 8-1, 8-2, 8-3, 8-4, 8-6, 8-7, 8-8, 8-9, 8-10, 8-11, 8-16 Problems 5, 9, 11, 12, 26, 31, 42, 43, 44, 46 2/6/2004 OFB Chapter 8 60