1 The Chemistry of Acids and Bases

2 Acid and Bases

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4 Some Properties of Acids Produce H + (as H 3 O + ) ions in water (the hydronium ion is a hydrogen ion attached to a water molecule) Taste sour Corrode metals Electrolytes React with bases to form a salt and water pH is less than 7 Turns blue litmus paper to red “Blue to Red A-CID”

5 Some Properties of Bases Produce OH - ions in water Taste bitter, chalky Are electrolytes Feel soapy, slippery React with acids to form salts and water pH greater than 7 Turns red litmus paper to blue “Basic Blue”

6 Some Common Bases NaOHsodium hydroxidelye KOHpotassium hydroxideliquid soap Ba(OH) 2 barium hydroxidestabilizer for plastics Mg(OH) 2 magnesium hydroxide“MOM” Milk of magnesia Al(OH) 3 aluminum hydroxideMaalox (antacid) Al(OH) 3 aluminum hydroxideMaalox (antacid)

7 Acid/Base definitions Definition #1: Arrhenius (traditional) Acids – produce H + ions (or hydronium ions H 3 O + ) acids can be classified as monoprotic, diprotic or triprotic Bases – produce OH - ions problem: some bases don’t have hydroxide ions Nice, simple definitions but has limitations… restricted to aqueous solutions couldn’t explain basic properties of NH 3

8 Acid/Base Definitions Definition #2: Brønsted – Lowry Acids – proton donor Bases – proton acceptor A “proton” is really just a hydrogen atom that has lost it’s electron!

9 A Brønsted-Lowry acid is a proton donor A Brønsted-Lowry base is a proton acceptor acid conjugate base base conjugate acid

10 Conjugate Pairs

11 Bronsted-Lowry A-B Because many A/B reactions are reversible, it is useful to identify conjugates (opposites) that will react in the reverse reaction conjugate A-B pairs = 2 formulas in an equation whose formulas differ by a H + strong A-B are not equilibrium expressions, but all other A-B are reversible

12 Acids & Base Definitions Lewis acid - accepts an electron pair Lewis base - donates an electron pair Definition #3 – Lewis

13 Lewis Acid/Base Reaction

14 Lewis Acid-Base Interactions in Biology The heme group in hemoglobin can interact with O 2 and CO.The heme group in hemoglobin can interact with O 2 and CO. The Fe ion in hemoglobin is a Lewis acidThe Fe ion in hemoglobin is a Lewis acid O 2 and CO can act as Lewis basesO 2 and CO can act as Lewis bases Heme group

15 Brønsted-Lowry vs. Lewis All B/L bases are Lewis bases BUT, by definition, a B/L base cannot donate its electrons to anything but a proton (H+) While B/L is most useful for our purposes, Lewis allows us to treat a wider variety of reactions (even if no H+ transfer occurs) as A/B reactions

16 HCl, HBr, HI, HNO 3, H 2 SO 4 HClO 3 and HClO 4 are the strong acids. Strong Acids/Bases The strength of an acid (or base) is determined by the amount of IONIZATION (Not pH value).

17 The strong bases are: alkali-metal hydroxides and alkaline earth metal hydroxides. Ex. NaOH, KOH, CsOH, Ca(OH) 2, etc. Note: The stronger the acid/base, the weaker its conjugate pair. Strong Acids/Bases

18 The pH scale is a way of expressing the strength of acids and bases. Instead of using very small numbers, we just use the NEGATIVE power of 10 on the Molarity of the H + (or OH - ) ion. Under 7 = acid 7 = neutral Over 7 = base

19 pH of Common Substances

20 20 pH and acidity 1.Acidity or Acid Strength depends on Hydronium Ion Concentration [H 3 O + ] 2.The pH system is a logarithmic representation of the Hydrogen Ion concentration (or OH - ) as a means of avoiding using large numbers and powers. pH = - log [H 3 O + ] pOH = - log [OH - ] 3.In pure water [H 3 O + ] = 1 x mol / L (at 25 o C)  pH = - log(1 x 10 -7) = - (0 - 7) = 7 4.pH range of solutions: pH 1 x m / L pH > 7 (Basic) [H 3 O + ] < 1 x m / L

21 pH calculations – Solving for H+ If the pH of Coke is 3.12, [H + ] = ??? Because pH = - log [H + ] then - pH = log [H + ] - pH = log [H + ] Take antilog (10 x ) of both sides and get 10 -pH = [H + ] [H + ] = = 7.6 x M

22 pOH Since acids and bases are opposites, pH and pOH are opposites!Since acids and bases are opposites, pH and pOH are opposites! pOH does not really exist, but it is useful for changing bases to pH.pOH does not really exist, but it is useful for changing bases to pH. pOH looks at the perspective of a basepOH looks at the perspective of a base pOH = - log [OH - ] Since pH and pOH are on opposite ends, pH + pOH = 14

23 pH [H + ] [OH - ] pOH

24 pH indicators Indicators are dyes that can be added that will change color in the presence of an acid or base. Some indicators only work in a specific range of pH Once the drops are added, the sample is ruined Some dyes are natural, like radish skin or red cabbage

25 25 Indicators

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27 Wait, water can go both ways? amphoteric substances can behave as either an acid or base depending on what they react with. water and anions with protons (H + ) attached are most common amphoterics

28 Autoionization of Water H 2 O + H 2 O OH - + H 3 O equilibrium K eq = [H 3 O + ] [OH - ] = so K eq becomes K w and equals 1.00 x at 25 o C In a neutral solution [H 3 O + ] = [OH - ]

29 Only partially ionize (less than 100%) in water.Only partially ionize (less than 100%) in water. Acids (symbol=HA)Acids (symbol=HA) equilibrium K eq = [H 3 O + ] [OH - ]/[HA] = so K eq becomes K a –The bigger the K a the stronger the acid –Polyprotic acids have more than 1 H+ available to ionize »Have multiple K a values ( K a1 K a2 K a3 ) »Always easier to remove 1 st H+ than 2 nd »If K a2 is different than K a1 by 10 3 (or more) consider only K a1 to get pH Weak Acids/Bases

30 Bases (symbol=B)Bases (symbol=B) –2 general categories »Contain neutral substances that have an atom with non-bonding electrons Ex. NH 3  NH 4 + »Anions of weak acids Ex. ClO-  HClO equilibrium K eq = [HB + ] [OH - ]/[B] = so K eq becomes K b Relationship between K a and K bRelationship between K a and K b –K a x K b = K w –pK a + pK b = pK w = Weak Acids/Bases

31 Equilibrium Constants for Weak Acids Weak acid has K a < 1 Leads to small [H 3 O + ] and a pH of 2 - 7

32 Equilibrium Constants for Weak Bases Weak base has K b < 1 Leads to small [OH - ] and a pH of 7-12

33 Relation of K a, K b, [H 3 O + ] and pH

34 Equilibria Involving A Weak Acid You have 1.00 M HA. Calc. the equilibrium concs. of HA, H 3 O +, A -, and the pH. HA + H 2 O H 3 O + + A - Step 1. Define equilibrium concs. in ICE table [HA] [H 3 O + ] [A - ] initialchangeequilib x+x+x 1.00-xxx

35 Equilibria Involving A Weak Acid Step 2. Solve equilibrium (K a ) expression This is a quadratic. Solve using quadratic formula. because K a for most weak acids is less than 10 -3, 1- x is about equal to 1, so K a = x 2 /1.00

36 Equilibria Involving A Weak Acid So the K a expression becomes Now we can more easily solve this approximate expression.

37 Equilibria Involving A Weak Acid Step 3. Calculate the pH x = [ H 3 O + ] = [ A - ] = 4.2 x M pH = - log [ H 3 O + ] = -log (4.2 x ) = 2.37

38 For each problem, identify if the short-cut is a valid method What is the pH of a 0.12 M solution of hypochlorous acid? What is the pH of a 0.12 M solution of lactic acid? What is the pH of 0.12 M solution of chlorous acid? What is the pH of a 0.12 M solution hydrochloric acid?

39 Equilibria Involving A Weak Base You have M of B. Calc. the pH. B + H 2 O OH - + HB + K b = 1.8 x Step 1. Define equilibrium concs. in ICE table [B][HB + ][OH - ] [B][HB + ][OH - ]initialchangeequilib x+x+x xx x

40 Equilibria Involving A Weak Base Step 2. Solve the equilibrium expression b/c K b for most weak bases is less than 10 -3, x is about equal to 0.010, so K b = x 2 /0.010 x = [OH - ] = [HB + ] = 4.2 x M and [B] = x ≈ M

41 Equilibria Involving A Weak Base Step 3. Calculate pH [OH - ] = 4.2 x M so pOH = - log [OH - ] = 3.37 Because pH + pOH = 14, pH = 10.63

42 A-B properties of salt solutions for the most part anions are slightly basic (because they attract protons) and cations are slightly acidic (because they can donate protons) Anions –Look at strength of the acid to which it is a conjugate –If acid is strong, anion won’t really take H+ from water –If acid is weak, anion will react to a small extent (  pH) –If amphoteric need to look at magnitudes of Ka and Kb Cations –Polyatomic cations can be the conjugate acid of a weak base –Usually react to make H 3 O+ (  pH)

43 Predict whether each of the following salts will result in an acidic, basic, or neutral solution when dissolved in water Fe(NO 3 ) 3 BaCl 2 NaHSO 4 LiF

44 A/B Behavior & Chemical Structure 1.Polarity -if H is the positive end = acid -if H is negative end (NaH) = base -if non-polar, neither acid or base 2.Strength of bond -Look at what H is bonded to -How easy is it to dissociate into ions? 3.Stability of conjugate: the greater the stability of the conjugate, the stronger the acid

45 A/B Behavior & Chemical Structure Binary Acids 1. HX bond strength is most important 2. acidity increases down a group - larger elements - longer and weaker bonds 3. in same row, look at bond polarity - across from L to Right increases EN - Across from L to R increases acidity

46 A/B Behavior & Chemical Structure Oxyacids (have O in compound) 1. Have same # of OH groups and the same # of O atoms, acid strength  with  in EN of center atom 2. Have same center atom (Y) acid strength  as the # of O atoms attached to Y  3. in a series of oxyacids, acidity  with as the oxidation # of the center atom 

47 A/B Behavior & Chemical Structure Carboxylic Acids (have –COOH in compound) 1.H on OH group is ionized -the other O atom draws elctron density away from OH bond increasing polarity -the conj. base (COO-) can exhibit resonance making it more stable 2.Acid strength of COOH group increases as the # of electronegative atoms in the acid increase.

48 Arrange the following series in order of increasing acid strength AsH 3, HI, NaH, H 2 O H 2 SeO 3, H 2 SeO 4, H 2 O

49 In each pair, choose the compound that leads to the more acidic solution HBr, HF PH 3, H 2 S HNO 2, HNO 3 H 2 SO 3, H 2 SeO 3