Ch Acids and Bases. Arrhenius Definition Acids produce hydrogen ions in aqueous solution. Bases produce hydroxide ions when dissolved in water.

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1 Ch Acids and Bases Arrhenius Definition Acids produce hydrogen ions in aqueous solution. Bases produce hydroxide ions when dissolved in water. Limits to aqueous solutions. Only one kind of base. NH 3 ammonia could not be an Arrhenius base. Bronsted-Lowry Definitions And acid is an proton (H + ) donor and a base is a proton acceptor. Acids and bases always come in pairs. HCl is an acid.. When it dissolves in water it gives its proton to water. HCl(g) + H 2 O(l) H 3 O + + Cl - Water is a base makes hydronium ion 1

2 Conjugate Acid Base Pairs General equation HA(aq) + H 2 O(l) H 3 O + (aq) + A - (aq) Acid + Base Conjugate acid +Conjugate base This is an equilibrium. Competition for H + between H 2 O and A - The stronger base controls direction. If H 2 O is a stronger base it takes the H + Equilibrium moves to right. Acid dissociation constant K a The equilibrium constant for the general equation. HA(aq) + H 2 O(l) H 3 O + (aq) + A - (aq) K a = [H 3 O + ][A - ] [HA] H 3 O + is often written H + ignoring the water in equation (it is implied). Acid dissociation constant K a HA(aq) + H 2 O(l) H 3 O + (aq) + A - (aq) means the same as HA(aq) K a = [H + ][A - ] [HA] H + (aq) + A - (aq) Strong acids dissociate completely. Equilibrium far to right. Conjugate base must be weak. What about weak acids? 2

3 Back to Pairs Strong acids K a is large [H + ] is equal to [HA] A - is a weaker base than water Weak acids K a is small [H + ] <<< [HA] A - is a stronger base than water Types of Acids Oxyacids (Ternary Acids) Polyprotic Acids Carboxylic Acids Binary Acids Structure and Acid Properties Any molecule with an H in it is a potential acid. The stronger the X-H bond the less acidic (compare bond dissociation energies). The more polar H-O-X bond -stronger acid. 3

4 Types of Acids Oxyacids - Proton is attached to the oxygen of an ion. The more polar the acid, the easier the H + comes off, the stronger the acid Strength of oxyacids The more oxygen hooked to the central atom, the more acidic the hydrogen. HClO 4 > HClO 3 > HClO 2 > HClO Remember that the H is attached to an oxygen atom. The oxygens are electronegative Pull electrons away from hydrogen Strength of oxyacids Electron Density Cl O H 4

5 Strength of oxyacids Electron Density O Cl O H Strength of oxyacids Electron Density O O Cl O H Strength of oxyacids Electron Density O O O Cl O H 5

6 Polyprotic Acids Types of acids Always dissociate stepwise. The first H + comes of much easier than the second. Ka for the first step is much bigger than Ka for the second. Denoted Ka 1, Ka 2, Ka 3 Types of Acids Polyprotic Acids- more than 1 acidic hydrogen (diprotic, triprotic). Strength of Polyprotic acids? Types of Acids Organic acids contain the Carboxyl group -COOH with the H attached to O Generally very weak. 6

7 Binary Acids In a covalent bond, the electrons from one atom attracted to the nucleus of the the other atom Bigger the molecule, the weaker the bond, the stronger the acid Binary Acids Amphoteric DEF Behave as both an acid and a base. Water autoionizes 2H 2 O(l) H 3 O + (aq) + OH - (aq) K W = [H 3 O + ][OH - ]=[H + ][OH - ] At 25ºC K W = 1.0 x10-14 This occurs in EVERY aqueous solution. Neutral solution [H + ] = [OH - ]= 1.0 x10-7 Acidic solution [H + ] > [OH - ] Basic solution [H + ] < [OH - ] 7

8 Identify the Amphoteric substance H 2 CO 3 H + + HCO - 3 Ka 1 = 4.3 x 10-7 HCO - 3 H + + CO -2 3 Ka 2 = 4.3 x ph= -log[h + ] ph and poh Used because [H + ] is usually very small As ph decreases, [H + ] increases exponentially Sig figs only the digits after the decimal place of a ph are significant Example [H + ] = 1.0 x sig figs total ph= sig figs to the right of the decimal point poh= -log[oh - ] Relationships K W = [H + ][OH - ]= 1.0 x = ph + poh [H + ],[OH - ],ph and poh Given any one of these we can find the other three. 8

9 [H + ] ph Acidic Neutral Basic poh Basic [OH - ] Equilibrium and Calculating ph of Solutions Always write down the major ions in solution. Remember these are equilibria. Remember the chemistry. Don t try to memorize there is no one way to do this. Strong Acids HBr, HI, HCl, HNO 3, H 2 SO 4, HClO 4 ALWAYS WRITE THE MAJOR SPECIES Completely dissociated [H + ] = [HA] [OH - ] is going to be small because of equilibrium = [H + ][OH - ] If [HA]< 10-7 water contributes H + 9

10 Calculate the ph of a strong acid With a high concentration super acid, ph <0 Ka will be small. Weak Acids ALWAYS WRITE THE MAJOR SPECIES. It will be an equilibrium problem from the start. Determine whether most of the H + will come from the acid or the water. Compare Ka or Kw Rest is just like last chapter. Calculate the ph of a weak acid Calculate the ph of 2.0 M acetic acid HC 2 H 3 O 2 with a Ka 1.8 x10-5 Calculate poh, [OH - ], [H + ] 10

11 A mixture of Weak Acids The process is the same. Determine the major species. The stronger will predominate. Bigger Ka if concentrations are comparable Calculate the ph of a mixture 1.20 M HF (Ka = 7.2 x 10-4 ) and 3.4 M HOC 6 H 5 (Ka = 1.6 x ) A mixture of Weak Acids Calculate the ph of a mixture 1.20 M HF (Ka = 7.2 x 10-4 ) and 3.4 M HOC 6 H 5 (Ka = 1.6 x ) Percent dissociation of an Acid = amount dissociated x 100 initial concentration For a weak acid percent dissociation increases as acid becomes more dilute. As [HA] 0 decreases [H + ] decreases but % dissociation increases. Le Chatelier 11

12 Percent dissociation of an Acid Calculate the % dissociation of 1.00 M Acetic acid (Ka = 1.8 x 10-5 ) Working Backwards What is the Ka of a weak acid that is 8.1 % dissociated as M solution? Bases The OH - is a strong base. Hydroxides of the alkali metals are strong bases because they dissociate completely when dissolved. The hydroxides of alkaline earths Ca(OH) 2 etc. are strong dibasic bases, but they don t dissolve well in water. Used as antacids because [OH - ] can t build up. 12

13 Bases without OH - Bases are proton acceptors. NH 3 + H 2 O NH OH - It is the lone pair on nitrogen that accepts the proton. Many weak bases contain N B(aq) + H 2 O(l) K b = [BH + ][OH - ] [B] BH + (aq) + OH - (aq) Strength of Bases Hydroxides are strong. Others are weak. Smaller K b weaker base. Calculate the ph of a solution of 4.0 M pyridine (Kb = 1.7 x 10-9 ) N: K a tells us K b The anion of a weak acid is a weak base. Calculate the ph of a solution of 1.00 M NaCN. Ka of HCN is 6.2 x The CN - ion competes with OH - for the H + 13

14 Anion of weak acid, cation of weak base K a > K b K a < K b K a = K b acidic basic Neutral 14

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