Arrhenius Model Acid. Base. Brønsted-Lowry Model Acid. Base. + H O: + H Cl: H O H + [ :Cl: ] -

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1 Chapter 14

2 1. Students will be able to define an acid and base in terms of both the Arrhenius and the Bronsted-Lowry definitions and provide examples of each (including examples that follow the Bronsted-Lowry definition better than the Arrhenius definition). 2. Students will be able to predict relative concentrations of species (HA, H +, A -, HB, B -, OH - ) in solution given K a for various solutions including: a) An acid dissolved in water. b) Two acids dissolved in water. c) An acid and a weak (Bronsted-Lowry base) in water. d) A polyprotic acid dissolved in water.

3 Arrhenius Model Acid Base Brønsted-Lowry Model Acid Base + H O: + H Cl: H O H + [ :Cl: ] - H H

4 H O: + H Cl: H O H + [ :Cl: ] - H H Acid Ionization Equation: or Acid Ionization Constant, Ka:

5 HA + H 2 O H 3 O + + A - NH 3 + HCl NH 4 Cl Conjugate acid Conjugate base HCN + Cl - <=> HCl + CN - H 2 S + F - <=> HF + HS - HBr + H 2 O <=> H 3 O + + Br -

6 Write the conjugate base for each of the following: 1. HF 2. H 2 S 3. HNO 2 4. C 6 H 5 COOH 5. NH 4 +

7 8. Students will be able to recognize all types of acids including: a) mineral acids ex. HF, HCl b) oxyacids ex. HNO 2, H 2 SO 3 c) organic acids ex. CH 3 COOH, C 6 H 5 COOH d) conjugate bases of polyprotic acids ex. HS -, HCO 3 - e) ammonium salts ex. NH 4 Cl (NH 4+ ), CH 3 CH 2 NH 3 Cl (CH 3 CH 2 NH 3 + f) hydrated metal ions ex. Cu(H 2 O) 4 2+

8 a. mineral acids ex. HF, HCl b. oxyacids ex. HNO 2, H 2 SO 3 c. organic acids ex. CH 3 COOH, C 6 H 5 COOH d. conjugate bases of polyprotic acids ex. HS -, HCO - 3 e. ammonium salts ex. NH 4 Cl (NH 4+ ) CH 3 CH 2 NH 3 Cl (CH 3 CH 2 NH 3+ ) f. hydrated metal ions ex. Cu(H 2 O) 2+ 4

9 Strong Acids {HNO 3,H 2 SO 4, HClO 4, HCl, HI, HBr} are fully ionized Weak acids are only partially ionized (mostly molecules).

10 1) Molecules containing an ionizable hydrogen HCHO 2 (aq) H + (aq) + CHO 2 - (aq) HB H + + B - H 2 SO 3 (aq) <==> H + (aq) + HSO 3 - (aq) 2) Anions containing an ionizable hydrogen HSO 4 - (aq) H + (aq) + SO 4 2- (aq) 3) Cations (NH 4 + and hydrated transition metal ions) NH 4 + <==> H + + NH 3 Cu 2+ (aq) is really Cu(H 2 O) 4 2+ Cu(H 2 O) 4 2+ <==> H + (aq) + Cu(H 2 O) 3 OH +1 (aq)

11 1. HF 2. CH 3 CH 2 COOH 3. NaOH 4. NH 3 5. H 2 SO 3 6. K + 7. HCO 3-8. Ni HNO CH 3 NH 3 Cl 11. Fe(H 2 O) 3+ 6

12 Ex: Write the equation for the ionization for each of the following weak acids. HClO (aq) C 2 H 5 NH 3 + Cr(H 2 O) 6 3+ (aq)

13 1. HCl = H + = Cl - 2. HCl > H + = Cl - 3. HCl > H + > Cl - 4. H + = Cl - > HCl

14 1. HF = H + = F - 2. HF > H + = F - 3. HF > H + > F - 4. H + = F - > HF

15 3. Students will be able to compare relative concentrations of H + given the concentration of the dissolved acid as well as any pertinent Ka values. 4. Students will be able to identify substances as acids/bases, or amphoteric. 5. Students will be able to compare the strength of an acid s conjugate base to the strength of water as a base. 6. Students will be able to compare the strength of base s conjugate acid to the strength of water as an acid. 7. Students will be able to identify (by name/formula) all six strong acids Students will be able to recognize all types of acids including: a) mineral acids ex. HF, HCl b) oxyacids ex. HNO 2, H 2 SO 3 c) organic acids ex. CH 3 COOH, C 6 H 5 COOH d) conjugate bases of polyprotic acids ex. HS -, HCO - 3 e) ammonium salts ex. NH 4 Cl (NH 4+ ), CH 3 CH 2 NH 3 Cl (CH 3 CH 2 NH + 3 f) hydrated metal ions ex. Cu(H 2 O) 2+ 4

16 3. Students will be able to compare relative concentrations of H + given the concentration of the dissolved acid as well as any pertinent Ka values. 4. Students will be able to identify substances as acids/bases, or amphoteric. 5. Students will be able to compare the strength of an acid s conjugate base to the strength of water as a base. 6. Students will be able to compare the strength of base s conjugate acid to the strength of water as an acid. 7. Students will be able to identify (by name/formula) all six strong acids Students will be able to recognize all types of acids including: a) mineral acids ex. HF, HCl b) oxyacids ex. HNO 2, H 2 SO 3 c) organic acids ex. CH 3 COOH, C 6 H 5 COOH d) conjugate bases of polyprotic acids ex. HS -, HCO - 3 e) ammonium salts ex. NH 4 Cl (NH 4+ ), CH 3 CH 2 NH 3 Cl (CH 3 CH 2 NH + 3 f) hydrated metal ions ex. Cu(H 2 O) 2+ 4

17 Since product ions (including H + ) are in the numerator: the larger the Ka, the the acid the smaller the Ka, the the acid The stronger the acid the the conjugate base. The weaker the acid the the conjugate base. The stronger the base the the conjugate acid. The weaker the base the the conjugate acid.

18 What s the CA of H 2 O? What s the CB of H 2 O? What s the CA of HS -? What s the CB of HS -? I - is the CA/ CB of HI. HSO 4 - is the CA/ CB of H 2 SO 4. HSO 4 - is the CA/ CB of SO 4 2-

19 1. How do the following [H+] compare? (Hint: Think about % ionization) 0.10 M HCl 0.10 M HBr 0.10 M HCl 0.10 M H 2 SO M HNO M HF 0.10 M CH 3 COOH 0.10 M HCN 1.> 2.< 3.= 2. Rank the following in order of increasing [H + ] HF, HNO 3, HCl, HNO 2 3. H 3 PO 4, HF, H 2 SO 4, HI, HS -

20 9. Students will be able to explain the ionization of acid in water in terms of a) relative concentrations of species (H 2 O molecules, H + ions, and OH - ions) in solution. b) Value of K w. c) H 2 O as an amphoteric substance - a conjugate base (of H 3 O + ) and a conjugate acid (of OH --). d) How concentrations of H + and OH - would change (and thus ph) if the temperature of the solution would change. e) Equal concentrations of H + and OH - making water neutral.

21 The self-ionization (autoionization) of water: K = In pure water: [H + ] = [OH - ] = 1.0 x C Thus [H + ] [OH - ] 25 C ph = - log [H + ] [H + ] = 10 -ph Neutral [H + ] [OH - ] Acidic [H + ] [OH - ] Basic [H + ] [OH - ] 25 C

22 1) What s the ph of neutral C? 2) The ionization of water is endothermic. If temp. increases, K w. What s the ph of neutral water if K w = 1.0 x 40 C? Is water still neutral? Acid and base solutions are dissolved in water, so the above constant can always be used to determine [H + ] or [OH - ] if you know one. If [H + ] increases, then [OH - ]. (think LeChatelier)

23 9. Students will be able to interconvert between [H + ], [OH - ], ph, and poh.

24 Kw = [H + ] [OH - ] = 1.0 x ph = poh = ph + poh = [H + ] ph [OH - ] poh

25

26

27 Solution [H+] [OH-] ph poh M HCl M HNO x M HBr x M NaOH 1.0 x

28 Solution [H+] [OH-] ph poh 0.10 M Ca(OH) x M HCl x x 10-9 M HCl 1.0 x 10-7 (major contributor of H+ is H 2 O) 1.0 x Q - The ph of M HCl is What s the ph of a solution that s twice as acidic? H+ doubles ( M, thus ph = 2.70)

29 At any point: K = [H + ] [OH - ] 14 = ph + poh At the neutral Line: ph = 7 = poh Use a ruler to find other corresponding points. Ex. ph = 3.3 [H + ] = 5 x 10-4 M [OH - ] = 2 x poh = 10.7 and ph = 12.4 [H + ] = 4 x M [OH - ] = 2.3 x 10-2 poh = 1.6

30 Property Strong Acid Weak Acid Ka value large/small large/small (R/P favored) (R/P favored) Position of the far to the right/left far to the left dissociation equil. Equil. [H+] compared [H+] = [HA] [H+] << [HA] to orig. conc. HA 0.10 M HCl -> 0.10 M H M CH 3 COOH - > ~0.005 M H+ Strength conj. stronger/weaker stronger/weaker base compared than water than water to water

31 Oxyacids: acid in which the acidic proton is attached to an oxygen atom. Organic Acids: O R - C - O - H

32 Organic Bases: amines - contain nitrogen (ammonia derivatives) (see pg.647)

33 10. Students will be able to calculate the pka of an acid (given Ka) and relate pka to the strength of an acid.

34 pka is another method used to express the value of the Ka pka = - log 10 Ka The larger the pka, the weaker the acid. Example: 3 acids have the following Ka s Acid Ka pka HA 2.5 x HB 8.9 x HC 1.3 x Which is the strongest? Which is the weakest? HB (highest Ka, lowest pka HC (lowest Ka, highest pka)

35 12. Students will be able to predict the strength of an oxyacid based on its structure (i.e. number of oxygens or relative electronegativity of the central atom).

36 The more oxygen atoms in an acid, the stronger the acid. More oxygens in the center of an oxyacid draws the electron density away from the bond to Hydrogen, polarizing the bond, making it easier to ionize in water. The more electronegative the central atom, the stronger the acid. More electronegative is the central atom of an oxyacid draws the electron density away from the bond to Hydrogen, polarizing the bond, making it easier to ionize in water.

37 13. Students will be able to list all properties of acids and bases discussed in class.

38 Acid - produces H +, hydrogen ion in solution, H + (aq) = H 3 O + Common properties: 1. Reacts with active metals to form H 2 (g) 2. Reacts with metal carbonates to form CO 2 (g) 3. Turns litmus from blue to red 4. Sour taste

39 Base - Produces OH -, hydroxide ions in solution Common properties: 1. feels slippery - dissolve skin 2. Turns litmus from red to blue 3. Bitter taste

40 Problem Set M HCl [H + ] = 0.10 M CH 3 COOH [H + ] = 1) Find ph of M acetic acid, CH 3 COOH, CH 3 COOH H + + CH 3 COO - K a = 1.8 x 10-5

41 3) Find ph of M acetic acid, CH 3 COOH, K a = 1.8 x 10-5 CH 3 COOH H + + CH 3 COO - K a = 1.8 x 10-5

42 2) A M solution of a weak acid has ph = Calculate K a. HB (aq) <==> H + (aq) + B - (aq)

43 Since x << then x this eliminates the quadratic. Values of Ka are only ± 5 % accurate. Thus approximate methods may be used if less than 5% ionization. Percent Dissociation =

44 4) Find [H + ] of M soln of acid w/ K a 4.0 x 10-3 HB H + + B - Ka = [H+][B-] = 4.0 x 10-3 [HB]

45 4) Find [H + ] of M soln of acid w/ K a 4.0 x 10-3 HB H + + B - Ka = [H+][B-] = 4.0 x 10-3 [HB] % diss. = If % dissociation is above 5% make correction for equil [HB] using the approximate answer for [H + ] and recalculate a new [H + ]. ALWAYS CHECK ASSUMPTION BY FINDING % DISSOCIATION.

46 HB + H 2 O <==> H 3 O + + B - % ionization depends on: 1) 2) For a given weak acid, the percent dissociation increases as the acid becomes more dilute. NOTE: Even though the percent dissociation increases, the [H+] decreases as the solution becomes more dilute.

47 All acid solutions contain water and an acid. We ignore the amount of H + ions that water contributes because it is significantly less that the amount of H + that is contributed by the acid. (Because water is a MUCH weaker acid.) If a solution contains two weak acids of very different strengths the strongest acid is assumed to be the dominant (only) producer of H +. Ex. In solution of M HCl, what are all the contributors of H +?

48 Ex. A. Calculate the ph of a solution that contains 1.00 M HCN (K a = 6.2 x ) and 5.00 M HNO 2 (K a = 4.0 x 10-4 ). B. Calculate the concentration of the cyanide ion (CN - ) in this solution at equilibrium. SOLN: Dominant Species: HNO 2, HCN, H 2 O A. B.

49 H 2 SO 3 (aq) <==> H + (aq) + HSO 3 - (aq) K a1 = 1.7 x 10-2 HSO 3 - (aq) <==> H + (aq) + SO 3 2- (aq) K a2 = 6.0 x 10-8 The acids formed in successive steps become progressively weaker. [H+] from the 2 nd or 3 rd acid is usually very small compared to [H + ] from 1 st acid. As a result it is not normally necessary to compute any but the first acid. (Note: in dilute solutions of H 2 SO 4 (less than 1.0 M) the second dissociation step can contribute significantly to [H + ].) - See Ex & pg

50 Ca(OH) 2 - slaked lime CaCO 3 - limestone CaO - lime Na 2 CO 3 - soda ash NaOH - lye

51 General: Weak base + water <==> conjugate acid + hydroxide Type (1) Molecules: NH 3 (aq) + H 2 O (aq) NH 4 + (aq) + OH - C 2 H 5 NH 2 (aq) + H 2 O (aq) C 2 H 5 NH OH - Type (2) Anions: {Conjugate bases of weak acids} F - (aq) + H 2 O (aq) HF (aq) + OH - (aq) ClO 2 - (aq) + H 2 O (aq) HClO 2 (aq) + OH - (aq)

52 Calculating the ph of a weak base solution is similar to calculating ph of a weak acid except: 1) Use the equation 2) Use K_ 3) x =

53 1) Molecules containing an ionizable hydrogen HCHO 2 (aq) H + (aq) + CHO 2 - (aq) HB H + + B - H 2 SO 3 (aq) <==> H + (aq) + HSO 3 - (aq) 2) Anions containing an ionizable hydrogen HSO 4 - (aq) H + (aq) + SO 4 2- (aq) 3) Cations (NH 4 + and hydrated transition metal ions) NH 4 + <==> H + + NH 3 Cu 2+ (aq) is really Cu(H 2 O) 4 2+ Cu(H 2 O) 4 2+ <==> H + (aq) + Cu(H 2 O) 3 OH+ 1 (aq)

54 Weak acid: HNO 2 (aq) H + (aq) + NO - 2 (aq) K a = 6.0 x 10-4 Weak base: NO - 2 (aq) + H 2 O (aq) HNO 2 (aq) + OH - (aq) K b = 1.7 x In General: K a K b = K w This confirms: The strong the acid the its conjugate base.

55 Solution Acidic/Basic Use Ka/Kb Look up/calculate? M HF M KNO M CH 3 NH M NH 4 I M HNO M C 2 H 5 NH 3 Cl M NaCN

56 Example 1 - Find ph for M solution of C 2 H 5 NH 2 (K b = 5.6 x 10-4 ) 1 = = = = 11.87

57 Example 2 - Find ph for M solution of NaCN (K a HCN = 6.2 x ) 1 = = = = 11.10

58 Define - A salt is an ionic compound containing a cation other than H + and an anion other than OH - or O 2-. NOTE: Acid + Base Water + salt Video To determine acid-base properties of a salt you must consider the effects of cation and anion separately. Then combine these effects to give the overall result.

59 A.) Cations 1. Neutral 2. Acidic 3. Basic -

60 B.) Anions 1. Neutral 2. Acidic 3. Basic -

61 To determine if a compound is acidic/basic, analyze each ion separately - If it has both acid and base parts, check Ka and Kb values.the strong will dominate Acidic/Basic/Neutral? HF BaBr 2 MnCl 2 Mg(OH) 2 NH 4 NO 2 NaCN HNO 3 NaNO 3 KCl FeS NH 4 C 2 H 3 O 2 NH 4 ClO K a NH 4 + = 5.6 x K b ClO - = 3.6 x 10-7 K b C 2 H 3 O 2 - = 5.6 x K a HNO 2 = 4.0 x 10-4

62 a. NH 3 b. NaNO 2 c. KClO 4 d. Mg(NO 3 ) 2 e. C 2 H 5 NH 3 F

63 Lewis Model - An acid-base reaction involves an electron pair transfer. Lewis acid: e- pair (must have an empty valence) Lewis base: e- pair (must have an unshared e- pair) Ex. H + + NH 3 More examples continued next slide.

64 HCN + F - BCl 3 + NH 3 Mg 2+ + H 2 O **Lewis Model of Acid/Bases is used commonly in organic chemistry.**

65 A lewis base is also called a. Coordination Number = the number of ligands which attach to the lewis acid The number of ligands which attach to the lewis acid is typically Common ligands include:,,, ex. Al 3+ + CN - Zn(OH) 2 + OH -

66 Model Acid Base Arrhenius increases [H + ] increases [OH - ] Lowry proton donor/acceptor proton donor/acceptor -Bronsted Lewis donor/acceptor e- pair donor/acceptor e- pair

67 The stronger the acid the better/worse it loses its H + thus the stronger/weaker the bond to hydrogen. 1) Electronegativity of the central atom The more electronegative the central atom the stronger/weaker the acid. 2) The number of oxygen atoms around the central atom The more oxygens around the central atom the stronger/weaker the acid.

68 KEY: The weaker the bond to hydrogen, the stronger the acid. - The more oxygens or - The more electronegative the central atom in an oxyacid the more the electron density is drawn away from the bond to hydrogen, thus weakening the bond.

69 Base Anhydride: metal oxide metal oxide + water --> base (base anhydride) Na 2 O + H 2 O --> BaO+ H 2 O -->

70 Acid Anhydride: nonmetal oxide + water --> acid (acid anhydride) CO 2 + H 2 O --> SO 2 + H 2 O --> NOTE: To check if you ve written your acid/base correctly. Check to see that the oxidation number of the central atom is the same on both sides. This is a combination reaction not an oxidation-reduction reaction.

71 Formation of a salt: metal oxide + nonmetal oxide --> salt ex. CaO + CO 2 --> Na 2 O + P 2 O 5 --> BaO + N 2 O 5 -->

72 Decomposition of acids and bases: This is the reverse of the above reactions Base + ex. Ca(OH) 2 Acid + ex. H 2 SO 3

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