Types of Reactions. What are Acids &Bases? Chapter 15. Acids & Bases. Definition? a) Arrhenius. b) Bronsted-Lowry. c) Lewis

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1 Chapter 15. Acids & Bases Acid/Base Definitions Types of Acids/bases Polyprotic Acids The Ion Product for Water The ph and Other p Scales Aqueous Solutions of Acids and Bases Hydrolysis The Common Ion Effect Buffer Solutions Indicators and Titrations Types of Reactions a) Precipitation Reactions. Ionic compounds or salts b) Acid/base Reactions. Acids and Bases c) Redox Reactions. Oxidizing & Reducing agents What are Acids &Bases? Definition? a) Arrhenius b) Bronsted-Lowry c) Lewis

2 Acid Base Arrhenius definitions Anything that produces hydrogen ions in a water solution.» HCl (aq) H + + Cl - Anything that produces hydroxide ions in a water solution.»naoh(aq) Na + + OH - Arrhenius definitions are limited to aqueous solutions. Acid base reactions: HCl(aq) + NaOH(aq) NaCl(aq) + H 2 O(l) Brønsted-Lowry definitions Expands the Arrhenius definitions Acid Proton donor Base Proton acceptor This definition explains how substances like ammonia can act as bases. NH 3 (g) + H 2 O(l) NH OH - Eg. HCl(g) + NH 3 (g) > NH 4 Cl(s) HCl (acid), NH 3 (base). Lewis Definition Lewis was successful in including acid and bases without proton or hydroxyl ions. Lewis Acid: A substance that accepts an electron pair. Lewis base: A substance that donates an electron pair. E.g. BF 3 (g) + :NH 3 (g) F 3 B:NH 3 (s)

3 Types of Acids and Bases Binary acids Oxyacid Organic acids Acidic oxides Basic oxides Amine Polyprotic acids Binary Acids Compounds containing acidic protons bonded to a more electronegative atom. e.g. HF, HCl, HBr, HI, H 2 S The acidity of the haloacid (HX; X = Cl, Br, I, F) Series increase in the following order: HF <HCl<HBr< HI Oxyacids Compounds containing acidic - OH groups in the molecule. Acidity of H 2 SO 4 is greater than H 2 SO 3 because of the extra O (oxygens) The order of acidity of oxyacids from the a halogen (Cl, Br, or I) shows a similar trend. HClO 4 > HClO 3 > HClO 2 >HClO perchloric chloric chlorus hyphochlorus

4 Acidic Oxides These are usually oxides of nonmetallic elements such as P, S and N. E.g. NO 2, SO 2, SO 3, CO 2 They produce oxyacids when dissolved in water Basic Oxides Oxides oxides of metallic elements such as Na, K, Ca. They produce hydroxyl bases when dissolved in water. e.g. CaO + H 2 O --> Ca(OH) 2 Protic Acids Monoprotic Acids: The form protic refers to acidity or protons. Monoprotic acids have only one acidic proton. e.g. HCl. Polyprotic Acids: They have more than one acidic proton. e.g. H 2 SO 4 - diprotic acid H 3 PO 4 - triprotic acid.

5 Amines Class of organic bases derived from ammonia NH 3 by replacing hydrogen by organic groups. They are defined as bases similar to NH 3 by Bronsted or Lewis acid/base definitions. What acid base concepts (Arrhenius/Bronsted/Lewis) would best describe the following reactions: a) HCl(aq) + NaOH(aq) ---> NaCl(aq) + H 2 O(l) b)hcl(g) + NH 3 (g) ---> NH 4 Cl(s) c)bf 3 (g) + NH 3 (g) ---> F 3 B:NH 3 (s) d)zn(oh) 2 (s) + 2OH - (aq) ---> [Zn(OH) 4 ] 2- (aq) Common acids and bases Acids Formula Molarity* nitric HNO 3 16 hydrochloric HCl 12 sulfuric H 2 SO 4 18 acetic HC 2 H 3 O 2 18 Bases ammonia NH 3 (aq) 15 sodium hydroxide NaOH solid Page 139. Strong acids & bases

6 Acids and bases Acidic Basic Citrus fruits Baking soda Aspirin Detergents Coca Cola Ammonia cleaners Vinegar Tums and Rolaids Vitamin C Soap Dissociation Equilibrium, HCl(aq) + H 2 O(l) H 3+ O(aq) + Cl - (aq) H 2 SO 4 (aq) + H 2 O(l) H 3+ O(aq) + HSO 4- (aq) H 2 O(l) + H 2 O(l) H 3+ O(aq) + OH - (aq) This dissociation is called autoionization of water. HC 2 H 3 O 2 (aq) + H 2 O(l) H 3+ O(aq) + C 2 H 3 O 2- (aq) NH 3 (aq) + H 2 O(l) NH 4+ + OH - (aq) Brønsted-Lowry definitions Conjugate acid-base pairs. Acids and bases that are related by loss or gain of H + as H 3 O + and H 2 O. Examples. Acid Base H 3 O + H 2 O HC 2 H 3 O 2 C 2 H 3 O 2 - NH 4 + NH 3 H 2 SO 4 HSO 4 - HSO 4- SO 4 2-

7 Bronsted acid/conjugate base and base/conjugate acid pairs in acid/base equilibria HCl(aq) + H 2 O(l) H 3+ O(aq) + Cl - (aq) HCl(aq): acid H 2 O(l): base H 3+ O(aq): conjugate acid Cl - (aq): conjugate base H 2 O/ H 3+ O: base/conjugate acid pair HCl/Cl - : acid/conjugate base pair Select acid, base, acid/conjugate base pair, base/conjugate acid pair H 2 SO 4 (aq) + H 2 O(l) acid base conjugate acid conjugate base base/conjugate acid pair acid/conjugate base pair H 3+ O(aq) + HSO 4- (aq) Equilibrium, Constant, K a & K b K a : Acid dissociation constant for a equilibrium reaction. K b : Base dissociation constant for a equilibrium reaction. Acid: HA + H 2 O H 3+ O + A - Base: BOH + H 2 O B + + OH - [H 3+ O][ A - ] [B + ][OH - ] K a = ; K b = [HA] [BOH]

8 What is K a HCl(aq) + H 2 O(l) <===> H 3+ O(aq) + Cl - (aq) E.g. K a HCl(aq) + H 2 O(l) [H 3+ O][Cl-] K a = [HCl] [H + ][Cl-] K a = [HCl] H 3+ O(aq) + Cl - (aq) What is K a1 and K a2? H 2 SO 4 (aq) + H 2 O(l) H 3+ O(aq) + HSO 4- (aq) HSO 4- (aq) + H 2 O(l) H 3+ O(aq) + SO 4 2- (aq)

9 What is K b NH 3 (aq) + H 2 O(l) NH 4+ + OH - (aq) E.g. of K a H 2 SO 4 (aq) + H 2 O(l) HSO 4- (aq) + H 2 O(l) H 3+ O(aq) + HSO 4- (aq) H 3+ O(aq) + SO 4 2- (aq) [H 3+ O][HSO 4- ] H 2 SO 4 ; K a1 = [H 2 SO 4 ] [H 3+ O][SO 4 2-] H 2 SO 4 ; K a2 = [HSO 4- ] E.g. HC 2 H 3 O 2 (aq) + H 2 O(l) H 3+ O(aq) + C 2 H 3 O 2- (aq [H + ][C 2 H 3 O 2- ] H C 2 H 3 O 2 ; K a = [H C 2 H 3 O 2 ] NH 3 (aq) + H 2 O(l) NH 4+ + OH - (aq) [NH 4+ ][OH - ] NH 3 ; K b = [ NH 3 ]

10 Which is weaker? a. HNO 2 ; K a = 4.0 x b. HOCl 2 ;K a = 1.2 x c. HOCl ; K a = 3.5 x d. HCN ; K a = 4.9 x WEAKER/STRONGER Acids and Bases & K a and K b values A larger value of K a or K b indicates an equilibrium favoring product side. Acidity and basicity increase with increasing K a or K b. pk a = - log K a and pk b = - log K b Acidity and basicity decrease with increasing pk a or pk b. Autoionization of water Autoionization When water molecules react with one another to form ions. H 2 O (l) + H 2 O (l) H 3 O + (aq) + OH- (aq) (10-7 M) (10-7 M) K w = [ H 3 O + ] [ OH - ] = 1.0 x at 25 o C ion product of of water

11 What is K w? H 2 O(l) + H 2 O(l) H 3+ O(aq) + OH - (aq) This dissociation is called autoionization of water. Autoionization of water: K w = [H 3+ O][OH - ] K w is called ionic product of water K w = 1 x Why is water important for acid/base equilibria? Water is the medium/solvent for acids and bases. Acids and bases alter the dissociation equilibrium of water based on Le Chaterlier s principle H 2 O(l) + H 2 O(l) H 3+ O(aq) + OH - (aq) Comparing K w and K a & K b Any compound with a K a value greater than K w of water will be a an acid in water. Any compound with a K b value greater than K w of water will be a base in water.

12 ph and other p scales We need to measure and use acids and bases over a very large concentration range. ph and poh are systems to keep track of these very large ranges. ph = -log[h 3 O + ] poh = -log[oh - ] ph +poh = 14 ph scale A logarithmic scale used to keep track of the large changes in [H + ] M 10-7 M 1 M Very Neutral Very Basic Acidic When you add an acid, the ph gets smaller. When you add a base, the ph gets larger. ph of some common materials Substance ph 1 M HCl 0.0 Gastric juices Lemon juice Classic Coke 2.5 Coffee 5.0 Pure Water 7.0 Blood Milk of Magnesia 10.5 Household ammonia M NaOH 14.0

13 What is ph? K w = [H 3+ O][OH - ] = 1 x [H 3+ O][OH - ] = 10-7 x 10-7 Extreme cases: Basic medium [H 3+ O][OH - ] = x 10 0 Acidic medium [H 3+ O][OH - ] = 10 0 x ph value is -log[h + ] spans only 0-14 in water. ph, pk w and poh The relation of ph, K w and poh K w = [H + ][OH - ] log K w = log [H + ] + log [OH - ] -log K w = -log [H + ] -log [OH - ] ; previous equation multiplied by -1 pk w = ph + poh; pk w = 14 since K w =1 x = ph + poh ph = 14 - poh poh = 14 - ph Strong acids Acid and Base Strength Ionize completely in water. HCl, HBr, HI, HClO 3, HNO 3, HClO 4, H 2 SO 4. Weak acids Strong bases Weak bases Partially ionize in water. Most acids are weak. Ionize completely in water. Strong bases are metal hydroxides - NaOH, KOH Partially ionize in water.

14 ph and poh calculations of acid and base solutions a) Strong acids/bases dissociation is complete for strong acid such as HNO 3 or base NaOH [H + ] is calculated from molarity (M) of the solution b) weak acids/bases needs K a, K b or percent(%)dissociation ph of Strong Acid/bases HNO 3 (aq) + H 2 O(l) H 3 +O(aq) + NO 3- (aq) Therefore, the moles of H + ions in the solution is equal to moles of HNO 3 at the beginning. [HNO 3 ] = [H + ] = 0.2 mole/l ph = -log [H+] = -log(0.2) ph = ph of 0.5 M H 2 SO 4 Solution H 2 SO 4 (aq) + H 2 O(l) HSO 4- (aq) + H 2 O(l) H 3+ O(aq) + HSO 4- (aq) H 3+ O(aq) + SO 4 2- (aq) [H 3+ O][HSO 4- ] H 2 SO 4 ; K a1 = [H 2 SO 4 ] [H 3+ O][SO 4 2- ] H 2 SO 4 ; K a2 = ; K a2 ignored [HSO 4- ]

15 ph of 0.5 M H 2 SO 4 Solution H 2 SO 4 (aq) + H 2 O(l) H 3+ O(aq) + HSO 4- (aq) the moles of H + ions in the solution is equal to moles of H 2 SO 4 at the beginning. [H 2 SO 4 ] = [H + ] = 0.5 mole/l ph = -log [H + ] ph = -log(0.5) ph = x 10-2 M NaOH. 1.5 x 10-2 MNaOH. NaOH is also a strong base dissociates completely in water. [NaOH] = [HO - ] = 1.5 x 10-2 mole/l poh = -log[ho - ]= -log(1.5 x 10-2 ) poh = 1.82 As defined and derived previously: pk w = ph + poh; pk w = 14 ph = pk w +poh ph = 14 - poh ph = ; ph = 12.18

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