Acids and Bases. Chapter 18. The effects of acid rain on a statue of George Washington taken in 1935 (left) and 2001 (right) marble.

Transcription

1 Acids and Bases Chapter 18 The effects of acid rain on a statue of George Washington taken in 1935 (left) and 2001 (right) marble. CaCO3(s) + 2HCl(aq) ==> H2O(l) + CO2(g) + CaCl2(aq)

2 Stuff I need the Exam 1 in my box by Friday. Those who don t turn it in will use the Make-Up Exam for Exam 1. March 10 Exam 3 (Chapter 18/19) March 17 Make-Up Exam (Comprehensive + 20) Final Exam (Comprehensive) March 24 7:30-9:30AM

3 Acids and bases have distinct properties. Acids: Acrid sour taste React with metals (Group I,II) to yield H 2 gas Changes plant dye litmus from blue to red React with carbonates and bicarbonates to produce CO2 gas 200 Million MT H 2 SO 4 Acid Base Bases: Bitter taste Slippery feel 50 Million MT NaOH/yr 3 million containers Changes plant dye litmus from red to blue React and neutralizes the effects of acids

4 Acids and bases are everywhere. Common Acids, soft drinks Most anti-perspirants, water treatment plants, paper Common Bases

5 have three definitions

6 Chemistry uses three definitions of acids and bases: 1) Arrehenius 2) Bronsted-Lowry 3) Lewis Name Acid Definition Base Definition Arrhenius Substance that increases H + Substances that increase OH - Brønsted- Lowry Substances that donate H + Substances that accept H + Lewis Electron-pair acceptor Electron-pair donar

7 Arrhenius Acids and Bases Acid: a substance that has a H atom in its formula, and releases a proton H + when dissolved in water. HCl(g), HBr(g), HI (g), HNO3(l), H2SO4(l), HClO4(l) HCl(aq), HBr(aq), HI (aq), HNO3(aq), H2SO4(aq), HClO4(aq) H2O HA(g) <==> H + (aq) + A - (aq) Base: a substance that contains OH in its formula, and releases hydroxide ions (OH - ) when dissolved in water. NaOH(s), KOH (s), LiOH (s), Mg(OH)2(s), Ca(OH)2(s) NaOH(aq), KOH (aq), LiOH (aq), Mg(OH)2(aq), Ca(OH)2(aq) H2O MOH(s) <==> OH - + M +

8 H + does not exist but we use it symbolically anyway. H + reacts with water to form the hydronium ion, H3O + H2O HA(g) <==> H + (aq) + A - (aq) HA(aq) <==> H + (aq) + A - (aq) HA(g) + H2O(l) <==> H3O + (aq) + A - (aq) Equivalent ways of expressing the same thing H + and H3O + are equivalent in chemistry.

9 Acid and base formation is represented in two ways semi-confusing ways. Don t let it distract you. 1. H2O HA(g) <==> H + + A - H2O MOH(s) <==> OH - + M + The lazy but convenient way. H 2 O written over arrow with H + as the acid. 2. HA(g) + H2O(l) <==> H3O + (aq) + A - (aq) MOH(s) + H2O(l) <==> OH - (aq) + M + (aq) + H2O Reacting with H 2 O in the equation with H 3 O as acid.

10 The equilibrium constant called Acid-Dissociation Constant, Ka quantifies the extent of acid dissociation (i.e. acid strength). H2O HA(g) <==> H + + A - K a = [H+ ][A - ] [HA] HA(g) + H2O(l) <==> H3O + (aq) + A - (aq) K a = [H 3O + ][A - ] [HA] stronger acid => higher [H 3 O + ] => product-favored => larger K a weaker acid => lower [H 3 O + ] => reactant-favored = lower K a

11 Strong acids and strong bases completely dissociate in water--ka >> 1. HA(g) + H 2 O(l) H 3 O + (aq) + A - (aq) Ka = [A- ][H3O + ] [HA] product-favored Before dissociation After dissociation H3O + HA HA H3O + A - Ka >>1

12 Because of complete dissociation, strong acids and strong bases conduct electricity and are strong electrolytes. HCl(aq) Uni-directional arrow used to heavily product-favored H + (aq) + Cl - (aq) Strong Strong HNO 3 (aq) H + (aq) + NO 3- (aq) H2SO 4 (aq) H + (aq) + HSO 4- (aq) NaOH(aq) Ca(OH)2(aq) Na + (aq) + OH - (aq) Ca 2+ (aq) + 2OH - (aq)

13 Weak acids and weak bases dissociate only to a slight extent in water Ka << 1. HA(aq) + H 2 O(l) H 3 O + (aq) + A - (aq) Ka = [A- ][H3O + ] [HA] reactant-favored Before dissociation After dissociation HA HA HA HA HA HA HA HA H3O + A -

14 Weak acids and weak bases do not dissociate to a large extent in solution and are weak electrolytes (small value of Ka). Ka = [A- ][H3O + ] [HA] = << 1 All not strong is weak! HNO2 (aq) <=> NO2 - (aq) + H + (aq) CH3CO2H(aq) <=> CH3CO2 - (aq) + H + H2SO3 (aq) <=> HSO3 - (aq) + H + (aq)

15 Classify each of the following compounds as a strong acid, weak acid, strong base, or weak base. (a) H 2 SeO 4 (b) (CH 3 ) 2 CHCOOH (c) KOH (d) (CH 3 ) 2 CHNH 2 Pay attention to the text definitions of acids and bases. Look at O for acids as well as the -COOH group; watch for amine groups and cations in bases. (a) Strong acid - H 2 SeO 4 - the number of O atoms exceeds the number of ionizable protons by 2. (b) Weak acid - (CH 3 ) 2 CHCOOH is an organic acid having a -COOH group. (c) Strong base - KOH is a Group 1A(1) hydroxide. (d) Weak base - (CH 3 ) 2 CHNH 2 has a lone pair of electrons on the N and is an amine.

16 Acids can have one, two or three acidic protons depending on their structure. Monoprotic acids--only one H + available HCl H + + Cl - Strong electrolyte, strong acid HNO 3 H + + NO - 3 Strong electrolyte, strong acid CH 3 COOH H + + CH 3 COO - Weak electrolyte, weak acid Diprotic acids--two acidic H + available for reaction H 2 SO 4 H + + HSO 4 - HSO 4 - H + + SO 4 2- Strong electrolyte, strong acid Weak electrolyte, weak acid Triprotic acids--three acidic H + H 3 PO 4 H + + H 2 PO 4 - H 2 PO - 4 H + + HPO 2-4 HPO 2-4 H + + PO 3-4 Weak electrolyte, weak acid

17 Acid and bases react with one another in a neutralization reaction. NaOH(aq) + HCl(aq) <==> H2O + Na + + Cl - base + acid <==> Water + salt Net Ionic Equation: H + (aq) + OH - (aq) => H2O (aq) CH3COOH(aq) + NaOH (aq) <==> H2O + Na + + CH3COO - Weak acid + strong base <==> Water + salt

18 The Arrhenius acid-base definition fails to cover all cases..so chemists invented the Bronsted- Lowry definition. How Arrhenius Defintion Fails 1. NH3 or amines (like R-NH2) don t have OH group but are bases. 2. Many transition metals Cr, Al, Fe, Cu are acidic but have no H Arrhenius definition requires water...yet some acid base reactions occur without water as solvent. HCl(g) + NH3(g) => NH4Cl(s) gaseous without water

19 Acid-Base Reaction = Proton Transfer The Bronsted-Lowry concept views acids as proton donars and bases as proton acceptors.

20 An Bronsted acid is a substance that donates or a proton to a Bronsted base. A Bronsted base is a substance that accepts a proton from another a Bronsted acid. Conjugate Acid Conjugate Base Conjugate Acid Conjugate Base

21 For a molecule or ion to be a Bronsted base, it must have at least one unshared pair of electrons for accepting a proton. All of these have a lone-pair of e - and are bases! The Lone pairs are there if you draw the Lewis structure! H 2 O F - Cl - NH 3 OH - All can donate H + and are acids! H 2 O HF HCl HNO 3 HBr HClO4

22 Generalized Bronsted Acid and Base HA + B < > A BH + Acid a H + donor Base, a H + acceptor Conjugate Base Conjugate Acid Conjugate pair Conjugate pair A - is called the conjugate base of the acid HA. Has a free pair of electrons to accept a proton. BH + is called the conjugate acid of the base B Both are called conjugate acid-base pairs!

23 Amphoteric substances can act an Bronsted acid (proton donar) or a base (a proton acceptor). proton donar proton acceptor

24 Water is amphoteric,.it can act as a base or acid and depending on what it reacts with. Acid Base--H + acceptor Conjugate Acid Conjugate Base Solvent Base Acid--H + donar Base Acid

25 Identifying the following conjugate acid-base pairs (H + donars and H+ acceptors). conjugate take away H + + acid 1 base 2 base 1 + add H + acid 2 reaction 1 HF + H 2 O F - + H 3 O + reaction 2 HCOOH + CN - HCOO - + HCN reaction 3 NH CO 2-3 NH 3 + HCO - 3 reaction 4 H 2 PO OH - HPO H 2 O reaction 5 H 2 SO 4 + N 2 H + 5 reaction 6 HPO SO 2-3 HSO - + N 4 2 H 2+ 6 PO HSO - 3

26 Write the equilibrium expression nitrous acid (HNO 2 ) and explain its acidity in terms of a) the Arrhenius definition, and b) the Brønsted-Lowry acid base theory, c) identify the acid base conjugate pairs.

27 a) HNO 2 is an Arrhenius acid because it dissociates in water to produce H + ions: HNO 2 (aq) <===> H + (aq) + NO 2- (aq) b) Nitrous acid is a Brønsted-Lowry acid because it acts as a proton donor, transferring a proton to water to give hydronium ion The conjugate base of HNO 2 is NO 2-, the species that remains after HNO 2 has lost a proton

28 The stronger the acid (base) is, the weaker is its conjugate base (acid). HCl(g) + H2O(aq) <===> Cl - (aq) + H3O + (aq) very weak base NaOH(s) + H2O(l) <===> Na + + H2O + OH - very weak acid Weak acids (bases) give strong conjugate bases (acids). HCOOH + H2O <===> HCOO - + H3O + basic in water NH3(aq) + H2O(aq) <===> NH4 + (aq) + OH - (aq) acidic in water

29 The weaker the acid--the stronger its conjugate base. The stronger the acid--the weaker its conjugate base. Relative Strengths of Conjugate Acid-Base Pairs Acid (HA) Conjugate Base, A -

30 In which direction will these reactions proceed? H 2 SO 4 (aq) + NH 3 (aq) NH 4+ (aq) + HSO 4- (aq) HCO 3- (aq) + SO 4 2- (aq) HSO 4- (aq) + CO 3 2- (aq)

31 In which direction will these reactions proceed? H 2 SO 4 and NH 4 + are acids, NH 3 and HSO 4 - are bases. H 2 SO 4 is stronger acid than NH 4+, and NH 3 stronger base than HSO 4-, therefore NH 3 gets the proton H 2 SO 4 (aq) + NH 3 (aq) NH 4+ (aq) + HSO 4- (aq) stronger acid stronger base weaker acid weaker base HCO 3 - and HSO 4 - are acids, SO 4 2- and CO 3 2- are bases. HSO 4 - is the stronger acid, and CO 3 2- is the stronger base. Therefore, CO 3 2- gets the proton HCO 3- (aq) + SO 4 2- (aq) HSO 4- (aq) + CO 3 2- (aq) weaker acid weaker base stronger acid stronger bas

32 Kw is an equilibrium constant that describes the auto or self-ionization of water. H 2 O(l) H + (aq) + OH (aq) K w = [H + ][OH - ] H 2 O(l) + H 2 O(l) H 3 O + (aq) + OH (aq) Base Acid Acid Base K w = [H 3 O + ][OH - ] K w = [H3O + ][OH - ] = 1 X This equilibrium constant for water is called the Ion-Product of Water. Memorize the value.

33 The product of [H3O + ][OH - ] = 1 X a constant. Once we know one...we know the other! [H3O + ] [OH - ] Kw 1 X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X 10-14

34 [OH - ] and [H + ] can vary over 14 orders of magnitude [OH - ] Basic OH - > H3O + Neutral H3O + = OH - acidic H3O + > OH - [H3O + ] If we plot a few points of [OH - ] vs [H + ] then we see that we can not plot all the various powers of 10 that can exist in solution. In 1909, Sorenson suggests using a logarithmic plot and this makes things easy to see and to plot. It defines ph!

35 We can compress all 14 orders of magnitude using a logarithmic scale--called the ph scale! ph = -log [OH - ] Basic (ph > 7, poh < 7) Neutral (ph = 7, poh = 7) Acid (ph < 7, poh > 7) 14 orders of magnitude can be seen in a single graph! ph = -log [H3O + ]

36 ph is a defined logarithmic scale for measuring acidity. It is directly related to [H + ] concentration in solution. ph = -log [H + ] = -log [H3O + ] logarithmic form p = -log [H + ] = 10 -ph exponential form --1 ph unit represents a power of 10X of concentration (or an order of magnitude) as it is called.

37 Acidic, basic and neutral solutions are identified by their ph values [H3O + ] ph [OH - ] ph = -log [H3O + ] connect the dots K w = [H3O + ][OH - ] = The ion-product of water is a constant!

38 A solution with a ph of 4 is 10X lower in [H + ] than one with ph=3, 100X lower than ph=2 and 1000X lower than ph = 1. [H + ] -log[h + ] = (ph) 0.5M M M M Concentration changes by factor of 10, ph changes by +/- 1

39 Kw is related to ph via logarithm. K W = [H 3 O + ][OH - ]= 1.0 X take -log of both sides -log Kw = -log ([H 3 O + ][OH - ]) = -log(1.0 X ) -log K W = - log[h 3 O + ] + -log[oh - ] = -log (10-14 ) pk W = ph + poh = -(-14) pk W = ph + poh = 14 K W = [H 3 O + ][OH - ] = 10-14

40 [H3O + ] ph [OH - ] poh Relation ships between [H 3 O + ], ph, [OH - ] and poh

41 ph is measured with dyed paper or with a commercial instrument. ph meter ph (indicator) paper

42 The amounts of H3O + and OH - in aqueous solution determines whether a solution is acidic, neutral or basic. WHEN [H 3 O + ] > [OH - ] [H 3 O + ] = [OH - ] [H 3 O + ] < [OH - ] acidic solution ph < 7 neutral solution ph = 7 basic solution ph > 7 Litmus Paper Color

43 What is the concentration of OH - ions in a HCl solution whose hydrogen ion concentration is 1.3 M? Key: Strong acids dissociate completely-- stoichiometry dictates [H + ]. Memorize all strong acids (HCl, HBr, HI, HNO3, H2SO4, HClO4) [H + ] = 1.3 M K w = [H + ][OH - ] = 1.0 x [OH - ] = K w 1 x 10 [H + = -14 = 7.7 x 10 ] M

44 A research chemist adds a measured amount of HCl gas to pure water at 25 o C and obtains a solution with [H 3 O + ] = 3.0 x 10-4 M. Calculate [OH - ]. Is the solution neutral, acidic or basic? Again, strong acids dissociate completely-- stoichiometry dictates [H + ] SOLUTION: K w = 1.0 x = [H 3 O + ] [OH - ] [OH - ] = K w / [H 3 O + ] = 1.0 x /3.0 x 10-4 = 3.3 x M [H 3 O + ] > [OH - ]; the solution is acidic.

45 The ph of rainwater collected in a certain region of the northeastern United States on a particular day was What is the H + ion concentration of the rainwater? ph = -log [H + ] antilog(-ph) = antilog (log [H + ]) [H + ] = 10 -ph = = 1.5 x 10-5 M The OH - ion concentration of a blood sample is 2.5 x 10-7 M. What is the ph of the blood? ph + poh = poh = -log [OH - ] = -log (2.5 x 10-7 ) = 6.60 ph = poh = = 7.40

46 Log Knowing and the Exponential math can help you Forms go fast Logarithmic Form ph = -log [H 3 O + ] Exponential Form 10 -ph = [H 3 O + ] poh = -log [OH - ] 10 -poh = [OH - ] pk a = -log K a 10 -pka = pk a When H 3 O +, OH -, K a are large values----the pk s are small values. Strong acids have large H 3 O and K a therefore small ph and small pk a

47 Problem: Calculating [H 3 O + ], ph, [OH - ], and poh In a restoration project, a conservator prepares copper-plate etching solutions by diluting concentrated nitric acid, HNO 3, to 2.0 M, 0.30 M, and M HNO 3. Calculate [H 3 O + ], ph, [OH - ], and poh of the three solutions at 25 o C. For 2.0 M HNO 3, [H 3 O + ] = 2.0 M, and ph = -log [H 3 O + ] = = ph [OH - ] = K w / [H 3 O + ] = 1.0 x /2.0 = 5.0 x M; poh = For 0.3 M HNO 3, [H 3 O + ] = 0.30 M and -log [H 3 O + ] = 0.52 = ph [OH - ] = K w /[H 3 O + ] = 1.0 x /0.30 = 3.3 x M; poh = For M HNO 3, [H 3 O + ] = M and -log [H 3 O + ] = 2.20 = ph [OH - ] = K w / [H 3 O + ] = 1.0 x /6.3 x 10-3 = 1.6 x M; poh = 11.80

48 Acid-Base Equilibrium Problems Strong Acids/Bases 1 2 Weak Acid Weak Bases 100% dissociation No need for ICE table. [H 3 O + ] = [HA]. 1. Find K a /K b given equilibrium values 2. Find equilibrium values given K a Identify and write the correct equation 1. Simplify: If 100 x Ka/b < [A]0 then [HA] - x = [HA] 2. Look for perfect square 3. Quadratic equation

49 Know all strong acids and bases and you will recognize be able to recognize all weak acids/bases. hydrohalic acids perchloric nitric sulfuric Group I hydroxides Group II hydroxides

50 What is the ph of a 1.8 x 10-2 M Ba(OH) 2 solution? Ba(OH) 2 is a strong base 100% dissociation. 1 mol Ba(OH) 2 = 2 mol OH - OH - = 2 x 1.8 x 10-2 M = 0.36M pkw = ph + poh = ph = poh ph = (- log(0.036)) = 12.56

51 If an acid is a strong acid (base), it is 100% dissociated---easy for calculations of ph, poh. HCl + H2O > Cl - + H3O NaOH + H2O <-----> Na + + OH - Weak acids (bases) has reversible equilibrium we must use an ICE Table and algebra! HCOOH + H2O <------> HCOO - + H3O + NH3 + H2O <------> NH4 + + OH -

52 % ionization of an acid is the ratio of [H + ] at equilibrium to [HA]initial X 100. % ionization = [H + ]equilbrium [HA] inital x 100% % ionizationb = [OH - ]equilbrium [OH - ] inital x 100%

53 As the concentration of a weak acid (base) decreases, the % ionization (dissociation) of the acid (base) increases! % Ionization Strong Acid Weak Weak Acid Acid Rationale: larger solution volume accommodates more ions (analogous to pressure effects on gas equilibria when n gas is non-zero) K a = [H 3 O+ ][A - ] [HA] Acid Molarity K a = n n H 3 O + A - n HA 1 V

54 There are 2 key simplifications that can help us solve equilibrium problems rapidly. 1. [H 3 O + ] from the auto-ionization of water is negligible in comparison to H + from an acid, HA in solution. 2. If 100 x Ka < [HA]initial then [HA]initial - x = [HA] Why Does it Work? Because Ka values are known to about ± 5% accuracy. Check using the 5% Rule [H + ]equilbrium [HA] inital x 100 < 5% 3. If #2 fails then you must use the quadratic equation

55 Find the K a of a weak acid from the ph of its solution What is the K a of phenylacetic acid (HPAc)? HPAc(aq) + H 2 O(l) H 3 O + (aq) + PAc - (aq) initial x change -x - +x +x equilibrium x - x +(1 x 10-7 ) x K a = [H 3O + ][PAc - ] [HPAc] = [x + (10-7 ) ][x] [ x] = [x ] 2 [ x] Solution ph = 2.6 = -log[h3o + ] [H 3 O + ] = 10 -ph = = 2.5 x 10-3 M [H 3 O + ] [PAc - ] = x = 2.5 x 10-3 M >> 10-7 (the [H 3 O + ] contribution from water) [HPAc] eq = x = x M

56 K a = [H 3O + ][PAc - ] [HPAc] = [x ] 2 [ x] K a = (2.5 x 10-3 ) = 5.2 x 10-5

57 Determining concentrations and ph from K a and initial [HA] The ph of a solution originally containing M HF solution is What is the value of K a for HF at equilibrium? Initial Change Equilibrium [HF] = = M HF + H 2 O H 3 O + + F M -x M x K a = (9.2 x 10-3 ) 2 /0.241 = 3.52 x 10-4? M? M +x M +x M ph = = -log [H 3 O + ] K a = [H 3O + ][F ] [HF] 10 -ph = [H 3 O + ] = = 9.20 x 10-3 M x x

58 Determining concentrations from K a and initial [HA] Propanoic acid (CH 3 CH 2 COOH, simplified as HPr) is an organic acid whose salts are used to retard mold growth in foods. What is the [H 3 O + ] of a 0.10 M aqueous solution of HPr (K a of HPr = 1.3 x 10-5 )? PLAN: 1. Write a balanced equation for acid in water. 2. Write the equation for Ka. 3. Set-up and fill in the ICE Table 4. Use ph, initial solution concentration and ICE table to find K a.

59 HPr(aq) + H 2 O(l) H 3 O + (aq) + Pr - (aq) initial change -x - +x +x equilibrium x - x x K a = [H 3O + ][Pr - ] [HPr] = 1.3 x 10-5 = x x Can We Simplify? x = -b ± b 2 4ac 2a If No 100 x Ka < [HA]initial then [HA]initial - x = [HA] 100 x 1.3 x 10-5 < [.10]? Yes, it is:.10 - x = 0.10 K a = [H 3O + ][Pr - ] [HPr] = 1.3 x 10-5 = x

60 K a = [H 3O + ][Pr - ] [HPr] = 1.3 x 10-5 = x solving for x = 1.1 x 10-3 M = [H 3 O + ] Checking assumption with 5% Rule: If [H + ]equilibrium divided by [HA]initial (x 100) is < 5% then assumption is valid. %[HPr] diss = M 0.10M = 1.1% our assumption is valid << 5%

61 What is the ph of a 0.5 M HF solution given that Ka = 7.1 X 10-4 (at 25 C)? 1. Balanced equation for the acid + water reaction 2. Write Ka expression 3. Use ICE table to set up problem 4. Use simplifying assumptions when possible or use quadratic formula 5. Check assumption with 5% Rule

62 Initial (M) Change (M) Equilibrium (M) HF (aq) H + (aq) + F - (aq) x +x +x x x x K a = 7.1 x 10-4 = [H+ ][F - ] [HF] = x x Can we simplify? Ka x 100 < [HF]initial K a x 100 = 7.1 x 10-4 x 100 = 7.1 x 10-2 << [.50]: YES 0.50 x 0.50 K a x = 7.1 x 10-4 x 2 = 3.55 x 10-4 x = M = [H + ] = [F - ] = M ph = -log [H + ] = -log [0.019] = 1.72 [HF] = 0.50 x = 0.48 M

63 Is assumption (0.50 x 0.50) valid: pass the 5% rule? x = = [H + ]equilibrium and [HA]initial = 0.50M % ionization = M 0.50 M x 100% = 3.8% < 5% It s ok. What is the ph of a 0.05 M HF solution (at 25 0 C)? K a x = 7.1 x 10-4 x = M M 0.05 M x 100% = 12% More than 5% Approximation not ok. Must solve for x exactly using quadratic equation or method of successive approximation. Occurs at low concentrations as % ionization increases. -b ± b 2 4ac x = 2a

64 Polyprotic Acids

65 Polyprotic acids are acids that have more than one ionizable H + when reacted with water Phosphorous Acid (H 3 PO 3 ) Sulfurous Acid (H 2 SO 3 ) Phosphoric Acid Arsenic Acid (H 3 AsO 4 ) Each H has its own Ka The electronegativity of the bonded atoms influence the ionizability of an acidic hydrogen in a substance. Citric Acid (H 3 C 6 H 5 O 7 )

66 Phosphoric acid, H 3 PO 4 H 3 PO 4 (aq) + H 2 O(l) H 2 PO 4- (aq) + H 3 O + (aq) K a1 = [H 3O + ] [H 2 PO 4 - ] [H 3 PO 4 ] = 7.2 x 10-3 H 2 PO 4- (aq) + H 2 O(l) HPO 4 2- (aq) + H 3 O + (aq) K a2 = [H 3 O+ ] [HPO 4 2- ] [H 2 PO 4 - ] = 6.3 x 10-8 HPO 4 2- (aq) + H 2 O(l) PO 4 3- (aq) + H 3 O + (aq) K a3 = [H 3O + ] [PO 4 3- ] [HPO 4 2- ] K a1 > K a2 > K a3 = 4.2 x 10-13

67 The hydrolysis of ionic salts. Ionic Salt + Water ==>? ph

68 Acid and bases react with one another in a neutralization reaction. NaOH(aq) + HCl(aq) <==> H2O + Na + + Cl - base + acid <==> Water + salt Most salts can be viewed as coming from a parent acid and parent base. If the parents are strong the cation or anion will not react with water, if the parents are weak the ion will react with water in a process called hydrolysis. NaCl(s) Ca(NO3)(s) NH4Br(s) CH3COOK(s)

69 There are 4 acid-base neutralization reactions yielding salts that can react with water. 1. Strong acid + Strong base ==> Ionic salt + H2O HCl (aq) + NaOH (aq) ==> Na + + Cl - + H2O Neutral salt 2. Strong acid + Weak base ==> Ionic salt + H2O HBr (aq) + NH3 (aq) ==> NH4 + + Br - + H2O Acidic salt 3. Weak acid + Strong base ==> Ionic salt + H2O 2HCOOH (aq) + Ca(OH)2 (aq) ==> Ca HCOO - + 2H2O Basic Salt 4. Weak acid + Weak base ==> Ionic salt + H2O CH3COOH (aq) + NH3 (aq) ==> NH4 + + CH3COO - + H2O Depends on pka vs pkb

70 1. Salts formed from a strong acid and a strong base are neutral when dissolved in H2O. parent is NaOH a strong base parent is HCl a strong acid neither Na + or Cl - react with water. Neutral! NaCl(s) + H2O(l) <=> Na + (aq) + Cl - (aq) + H2O ph = 7 parent is KOH a strong base parent is H2SO4 a strong acid neither K + or SO4 - react with water. Neutral! K2SO4(s) + H2O(l) <=> K + (aq) + SO4 - (aq) + H2O ph = 7 Why? The anion of a strong acid (Cl -, I -, Br -, NO3 - ) is a much weaker base than water, and the cation of from the strong acid is a much weaker acid than water!

71 2. Solutions of salts formed from a strong acid and a weak base are acidic when dissolved in H2O. parent is NH4OH = weak base parent is HBr = strong acid cation will hydrolyze or react with water anion is from a strong acid and does not hydrolyze. NH 4 Br(s) NH 4 + (aq) + Br - (aq) NH 4 + (aq) + H2 O(l) NH 3 (aq) + H 3 O + (aq) hydrolysis gives acidic solution

72 3. Solutions of salts formed from a weak acid and a strong base are basic when dissolved in H2O. parent acid of the anion is CH3CO2H = weak acid parent of cation is KOH = strong base CH 3 COOK (s) H 2 O K + (aq) + CH 3 COO - (aq) anion hydrolyzible CH 3 COO - (aq) + H 2 O (l) CH 3 COOH (aq) + OH - (aq) hydrolysis of salt of weak acid gives a basic solution NaH 2 PO 4 (s) H 2 PO 4 - (aq) + H2 O(l) Na + (aq) + H 2 PO 4 - (aq) HPO 4 2- (aq) + H3 O + (aq)

73 4. Solutions of salts formed from a weak acid and a weak base depend on the Ka and Kb of the salt. Both are weak and thus cation and anion will hydrolyze. Which one wins depends on strength (Ka vs Kb) or the ions. Example: NH 4 HS NH + 4 (aq) + H 2 O NH 3 (aq) + H 3 O+ (aq) HS (aq) + H 2 O H 2 S(aq) + OH (aq) K a (NH + 4 ) = 5.7 x vs K b (HS - ) = 1.0 x 10-7 Since K b > K a, the solution is basic.

74 Summary of Hydrolyzed Salts in Water neutral (ph < 7) acidic (ph < 7) acidic (ph < 7) basic (ph > 7)

75 (a) KClO 4 (b) sodium benzoate, C 6 H 5 COONa (c) CrCl 3 (d) NaHSO 4 (a) The ions are K + and ClO 4-, which come from a strong base (KOH) and a strong acid (HClO 4 ). The solution will be neutral. (b) Na + comes from the strong base NaOH while C 6 H 5 COO - is the anion of a weak organic acid. The salt solution will be basic. (c) Cr 3+ is a small cation with a large + charge, so its hydrated form will react with water to produce H 3 O +. Cl - comes from the strong acid HCl. The salt solution will be acidic. (d) Na + comes from a strong base. HSO - 4 can react with water to form H 3 O +. The salt solution will be acidic.

76 You are given 0.1M solutions of the following. What is the nature of the solutions acid/ base/ neutral or amphoteric? KClO2 CsI NaHSO4 HCO2K Al(H2O)6 NaNO3 Na 3 PO 4 CH3COONH 4 FeCl3 Basic Neutral Acidic Basic Acidic Neutral Basic Depends on Ka vs Kb Acidic

77 Salts formed from a strong acid and a weak base hydrolyze in water to form acidic solutions. parent is NaOH = strong base parent is HCl = strong acid salt = neutral when dissolved NaCl(s) + H2O(l) <=> Na + (aq) + Cl - (aq) + H2O K2SO4(s) + H2O(l) <=> K + (aq) + SO4 - (aq) + H2O ph = 7 ph = 7 Why? The anion of a strong acid (Cl -, I -, Br -, NO3 - ) is a much weaker base than water, and the cation of from the strong acid is a much weaker acid than water!

78 Ka quantifies and communicates the degree of acid dissociation = an acids strength HA(aq) + H 2 O(l) H 3 O + (aq) + A - (aq) K a = [H 3O + ][A - ] [HA] strong acid = Ka is large, pka is small weak acid = Ka is small, pka is large HA H + HA HA HA H + H + HA HA H +

79 Kb is the equilbrium constant that quantifies a degree OH dissociation, a base s strength. B + H 2 O(l) BH + (aq) + OH - (aq) K b = [BH+ ][OH - ] [B] ---Strong bases dissociate completely Ca(OH)2(s) + H2O(l) ==> Ca 2+ (aq) + 2OH - (aq) + H2O(l) H2O NaOH(s) ====> Na + (aq) + Cl - (aq) ---Weak bases dissociate partially NH 3 (aq) + H 2 O (l) NH 4 + (aq) + OH - (aq) K b = 1.76 x 10-5 (CH3)2NH 2 (aq) + H 2 O (l) (CH3)2NH + (aq) + OH - (aq) K b = 5.4 x 10-4

80 KEY DOT CONNECTION: The Ka of an acid and the Kb of the acid s conjugate base are related through the ion-product constant of water. HA (aq) A - (aq) + H 2 O (l) H + (aq) + A - (aq) OH - (aq) + HA (aq) K a = [H+ ][A ] [HA] K b = [OH ][HA] [A ] H 2 O (l) H + (aq) + OH - (aq) K a K b = [OH ][H + ] If you know Ka for an acid you can determine Kb for its conjugate base! Kw = K a K b = pkw = pk a + pk b = 14

81 A table of bases and their conjugate acids, BH +. Notice! Kb x Ka = Kw = 1 x 10 14

82 Ka and Kb of Some Common Weak Acids and Base Acid Formula Ka Conjugate Kb Iodic acid HI 1.61 X 10-1 I X Chlorous Acid HClO2 1.1 X 10-2 ClO2-9.1 X Phosphoric Acid H3PO4 7.6 X 10-3 H2PO4-1.3 X Nitrous Acid HNO2 7.2 X 10-4 NO2-1.4 X Hydrofluoric Acid HF 6.6 X 10-4 F X Formic Acid HCOOH 1.8 X 10-4 HCO2-5.6 X Acetic Acid CH3CO2H 1.8 X 10-5 CH3CO2-5.6 X Hydrosulfuric Acid H2S 1.32 X 10-7 HS X 10-8 Hypochlorous Acid HClO 3.5 X 10-8 ClO X 10-7 Hydrazine N2H4 1.1 X 10-8 OH X 10-7 Water H2O 1.0 X 10-7 OH X 10-7 Ammonia NH3 5.6 X NH X 10-5 Hydrocyanic Acid HCN 4.0 X CN X 10-5 Dimethyl Amine (CH3)2NH 1.9 X (CH3)2NH X 10-4

83 Aqueous solutions of many metal ions are acidic because the hydrated metal ions transfers an H + ion to water. M(NO 3 ) n (s) + xh 2 O(l) M(H 2 O) x n+ (aq) + H 2 O(l) M(H 2 O) x n+ (aq) + nno 3- (aq) M(H 2 O) x -1OH (n-1)+ (aq) + H 3 O + (aq) high charge and small size enhance acidity

84 Predicting the relative acidity of weak-weak salt solutions Determine whether an aqueous solution of zinc formate, Zn(HCOO) 2, is acidic, basic, or neutral. The Ka for Zn (H2O)6 2+ = 10-9 and Ka for formic acid is 1.8 x SOLUTION: Both Zn 2 + and HCOO - come from weak conjugates. In order to find the relatively acidity, write the dissociation reactions and use the information in Tables 18.2 and Zn(H 2 O) 6 2+ (aq) + H2 O(l) HCOO - (aq) + H 2 O(l) Zn(H 2 O) 5 OH + (aq) + H 3 O + (aq) HCOOH(aq) + OH - (aq) K a Zn(H 2 O) 6 2+ = 1 x 10-9 K a HCOOH = 1.8 x 10-4 ; K b = K w /K a = 1.0 x /1.8 x 10-4 = 5.6 x K a for Zn(H 2 O) 6 2+ > Kb HCOO - ; the solution is acidic.

85 We solve weak base problems just like weak acid ones, except we solve for [OH-] instead of [H + ]. NH 3 (aq) + H 2 O (l) NH 4 + (aq) + OH - (aq) K b = [NH 4 + ][OH - ] [NH 3 ] For ammonia, K b = 1.76 x 10-5 what is the conjugate acid and what is it s pka? How would you write the reaction of NH4 + with water? Generalized Base Equilibria A - + H 2 O(l) AH + (aq) + OH - (aq) K b = [AH+ ][OH - ] [A - ] Perhaps the hardest part for students is writing the base reaction in water...just think proton donar and acceptor.

86 Morphine is a narcotic that is very effective at relieving intense pain. Morphine is produced as a weak base as it is water soluble in this form. What is the Kb, pkb if a M solution has a ph of 10.10? M(aq) + H2O(aq) <=> MH + (aq) + OH - (aq) initial change - -x +x +x equilibrium x - x x ph + poh = poh = ph = = 3.90 poh = -log [OH] [OH - ] = 10 -poh = = 1.26 x 10-4 K b = [MH+ ][OH ] [M] = [x 2 ] [.10M x] = ( ) 2 [ ] =

87 Determining ph from K b and initial [B] Dimethylamine, (CH 3 ) 2 NH, a key intermediate in detergent manufacture, has a K b = 5.9 x What is the ph of a 1.5 M aqueous solution of (CH 3 ) 2 NH? concentration (CH 3 ) 2 NH(aq) + H 2 O(l) (CH 3 ) 2 NH 2 + (aq) + OH - (aq) initial change - x - + x + x equilibrium x - x x K b = 5.9 x 10-4 = [(CH 3) 2 NH 2+ ][OH - ] [(CH 3 ) 2 NH] K b = [B initial] Simplify? > 100 K b K b = 5.9 x 10-4 = x K b = = x x [1.5] = 2542 > x = 3.0 x 10-2 M = [OH - ]

88 Check assumption: [3.0 x 10-2 M / 1.5 M] x 100 = 2% (error is < 5%; thus, assumption is justified) [H 3 O + ] = K w /[OH - ] = 1.0 x /3.0 x 10-2 = 3.3 x M ph = -log (3.3 x ) = 12.5

89 Sodium acetate (CH 3 COONa, abbreviated NaAc) has applications in photographic development and textile dyeing. What is the ph of a 0.25 M aqueous solution of NaAc? The K a of acetic acid (HAc) (conjugate acid of Ac) is 1.8 x concentration Ac - (aq) + H 2 O(l) initial change -x - +x +x equilibrium x - x x K b = [HAc][OH- ] K [Ac - w = ] K a HAc(aq) + OH - (aq) K w K a = K b = 1.0 x x 10-5 = 5.6 x 10-10

90 [Ac - ] = 0.25 M - x 0.25 M (since K b is small) Check assumption: [Ac - ]in / Kb > 100 =.25/ 5.6 x > 100 [HAc][OH - ] K b = [Ac - ] 5.6 x x 2 /0.25 M [OH - ] = x 1.2 x 10-5 M [H 3 O + ] = K w /[OH - ] [H 3 O + ] = K w /[OH - ] = 1.0 x /1.2 x 10-5 = 8.3 x M ph = -log (8.3 x M) = 9.1

91 Kw relates Ka of and acid and Kb of the conjugate base Kw Determine relates Ka the of ph and of acid a and M Kb solution of the conjugate of the salt base NaF if the Ka of HF is given as 6.80 X I C E F (aq) + H 2 O HF(aq) + OH (aq) 0.1M x x x (0.1-x) x x Can we simplify? [B] initial > 100 = M > 100 K b Kb = poh=5.92 ph=8.08

92 Quiz 6 Dimethylamine, (CH 3 ) 2 NH, a key intermediate in detergent manufacture, has a K b = 5.9 x What is the ph of a 1.5 M aqueous solution of (CH 3 ) 2 NH?

93 Equlibrium and Acid Strength

94 Molecular Structure and Its Connection to the Strength of an Acid The strength of an acid is connected to bond polarity (electronegativity) and bond strength.

95 The acid strength of non-metal hydrides increase across a period and down a group. Electronegativity increases Acid strength increases Use Weak HF to remember H2S H2Se H2Te Bond strength decreases, acid strength increases

96 The acid strength of a non-metal hydride increases across a period and down a group. Electronegativity increases, acidity strength increases Use Weak HF to remember H2S H2Se Bond strength decreases, acid strength increases H2Te

97 Oxo-acids are compounds composed of one or more acidic hydrogens bonded to oxygen atom which is further bound to another central atom, Z. O O O δ - δ + Z O H electronegative central atom Sulfuric Acid.. Sulfurous acid Phosphorous Acid

98 OXO-ACIDS: The greater electronegativity and number of internal atoms the more acidic the compound. electronegative central atom δ - δ + Z O H stable anion and acidic Z O - + H + Less acidic IIA IVA VA VIA VIIA H3BO3 H2CO3 HNO3 H2SiO4 H3PO4 H2SO4 HClO3 H3AsO4 H2SeO HBrO3 H6TeO6 More acidic HIO3 Electronegativity increases acidity increases More acidic Less acidic

99 The acidity of oxo-acids is determined by electronegativity (electron withdrawing effects). Acid Strength Increases Electronegativity Increases Very Weak Acid Strong Acid HClO < HClO 2 < HClO 3 < HClO 4 More oxygens, more electron-withdrawing, increase polarity and acidity

100 Indicate whether each is a strong or weak acid, predict the relative strengths of the following groups of oxoacids and the strengths of the conjugate base salts. a) HClO2, HBrO2, and HIO2. b) HIO HIO2, HIO3 c) HNO 3 and HNO 2. HClO2 > HBrO2, > HIO2. HIO < HIO2 < HIO3 HNO 3 > HNO 2. d) H 3 PO 3 and H 3 PO 4. H 3 PO 3 < H 3 PO 4. e) H2SO4 and H2SO3 H2SO4 > H2SO3

101 Many oxo-acids are polyprotic acids which have more than one ionizable H +. Phosphorous Acid (H 3 PO 3 ) Each H has its own Ka Sulfurous Acid (H 2 SO 3 ) Phosphoric Acid Arsenic Acid (H 3 AsO 4 ) The greater number of electronegative substituents the more acidic the acid is. Citric Acid (H 3 C 6 H 5 O 7 )

102 Each H + has its own Ka with Ka1 dictating chemistry H 3 PO 4 (aq) + H 2 O(l) H 2 PO 4- (aq) + H 3 O + (aq) K a1 = [H 3O + ] [H 2 PO 4 - ] [H 3 PO 4 ] = 7.2 x 10-3 H 2 PO 4- (aq) + H 2 O(l) HPO 4 2- (aq) + H 3 O + (aq) K a2 = [H 3O + ] [HPO 4 2- ] [H 2 PO 4 -] = 6.3 x 10-8 HPO 4 2- (aq) + H 2 O(l) PO 4 3- (aq) + H 3 O + (aq) K a3 = [H 3O + ] [PO 4 3- ] [HPO 4 2-] = 4.2 x K a1 > K a2 > K a3

103 A Lewis Acid is any substance that is an electronpair acceptor. Neutral Proton Donors H + BF 3 Lewis acids lack electrons and have an orbital. Some ewis Acids Cations Transition Metal Cations Al 3+, Ti 4+, Fe 3+, Zn 2+,

104 A Lewis Base is any substance that is an electronpair donor (nucleophile). H 2 O NH 3 O 2 2- Atoms having lone pairs of electrons is the distinguish ing feature

105 Identify the Lewis acids and Lewis bases in the following reactions: (a) H + + OH - H 2 O (b) Cl - + BCl 3 BCl - 4 (c) K + + 6H 2 O K(H 2 O) + 6 Look for electron pair acceptors (acids) and donors (bases). acceptor (a) H + + OH - donor H 2 O donor (b) Cl - + BCl 3 BCl - 4 acceptor (c) K + + 6H 2 O K(H 2 O) 6 + acceptor donor

106 Neutralization (in the Lewis acid context) occurs when a Lewis acid reacts and forms a covalent bond with a Lewis base. The bond is called a coordinate bond. acid base adduct The adduct contains a new covalent bond. adduct M 2 + H 2 O(l) M(H 2 O) 4 2+ (aq)