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Acids and Bases
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Acid/Base Definitions
Arrhenius Model Acids produce hydrogen ions in aqueous solutions Bases produce hydroxide ions in aqueous solutions Bronsted-Lowry Model Acids are proton donors Bases are proton acceptors
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Acid Dissociation Acid Proton Conjugate base HA H+ + A-
Alternately, H+ may be written in its hydrated form, H3O+ (hydronium ion)
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HNO2(aq) + H2O(l) NO2-(aq) H3O+(aq) Acid Base Conjugate base Conjugate acid NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) Base Acid Conjugate acid Conjugate base
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Dissociation of Strong Acids
Strong acids are assumed to dissociate completely in solution. Large Ka or small Ka? Reactant favored or product favored?
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Dissociation Constants: Strong Acids
Formula Conjugate Base Ka Perchloric HClO4 ClO4- Very large Hydriodic HI I- Hydrobromic HBr Br- Hydrochloric HCl Cl- Nitric HNO3 NO3- Sulfuric H2SO4 HSO4- Hydronium ion H3O+ H2O 1.0
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Dissociation of Weak Acids
Weak acids are assumed to dissociate only slightly (less than 5%) in solution. Large Ka or small Ka? Reactant favored or product favored?
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Dissociation Constants: Weak Acids
Formula Conjugate Base Ka Iodic HIO3 IO3- 1.7 x 10-1 Oxalic H2C2O4 HC2O4- 5.9 x 10-2 Sulfurous H2SO3 HSO3- 1.5 x 10-2 Phosphoric H3PO4 H2PO4- 7.5 x 10-3 Citric H3C6H5O7 H2C6H5O7- 7.1 x 10-4 Nitrous HNO2 NO2- 4.6 x 10-4 Hydrofluoric HF F- 3.5 x 10-4 Formic HCOOH HCOO- 1.8 x 10-4 Benzoic C6H5COOH C6H5COO- 6.5 x 10-5 Acetic CH3COOH CH3COO- 1.8 x 10-5 Carbonic H2CO3 HCO3- 4.3 x 10-7 Hypochlorous HClO ClO- 3.0 x 10-8 Hydrocyanic HCN CN- 4.9 x 10-10
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PROBLEM: Write the simple dissociation (ionization) reaction (omitting water) for each of the following acids. Hydrochloric acid (HCl) Acetic acid (HC2H3O2) The ammonium ion (NH4+) The anilinium ion (C6H5NH3+) The hydrated aluminum(III) ion [Al(H2O)6]3+
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Self-Ionization of Water
H2O + H2O H3O+ + OH- At 25, [H3O+] = [OH-] = 1 x 10-7 Kw is a constant at 25 C: Kw = [H3O+][OH-] Kw = (1 x 10-7)(1 x 10-7) = 1 x 10-14
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pH Scale
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Relationship between pH and pOH
Calculating pH, pOH pH = -log10(H3O+) pOH = -log10(OH-) Relationship between pH and pOH pH + pOH = 14 Finding [H3O+], [OH-] from pH, pOH [H3O+] = 10-pH [OH-] = 10-pOH
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pH and pOH Calculations
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Problem: Calculate [H+] or [OH-] as required for each of the following 25oC, and state whether the solution is neutral, acidic, or basic. 1.0 x 10-5M OH- 1.0 x 10-7M OH- 10.0M H+
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A Weak Acid Equilibrium Problem
What is the pH of a 0.50 M solution of acetic acid, HC2H3O2, Ka = 1.8 x 10-5 ? Step #1: Write the dissociation equation HC2H3O2 C2H3O2- + H+
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A Weak Acid Equilibrium Problem
What is the pH of a 0.50 M solution of acetic acid, HC2H3O2, Ka = 1.8 x 10-5 ? Step #2: ICE it! HC2H3O2 C2H3O2- + H+ I C E 0.50 - x +x +x x x x
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A Weak Acid Equilibrium Problem
What is the pH of a 0.50 M solution of acetic acid, HC2H3O2, Ka = 1.8 x 10-5 ? Step #3: Set up the law of mass action HC2H3O2 C2H3O2- + H+ E x x x
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A Weak Acid Equilibrium Problem
What is the pH of a 0.50 M solution of acetic acid, HC2H3O2, Ka = 1.8 x 10-5 ? Step #4: Solve for x, which is also [H+] HC2H3O2 C2H3O2- + H+ E x x x [H+] = 3.0 x 10-3 M
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A Weak Acid Equilibrium Problem
What is the pH of a 0.50 M solution of acetic acid, HC2H3O2, Ka = 1.8 x 10-5 ? Step #5: Convert [H+] to pH HC2H3O2 C2H3O2- + H+ E x x x pH = -log(3.0 x 10-3) = 2.52
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Percent Dissociation/Ionization
Amount dissociated (mol/L) = X 100% Initial concentration (mol/L) So….Calculate the percent dissociation for the previous problem. 60%? JK…How about 0.6%? Better? Tip of the day! For a given weak acid….the percent dissociation INCREASES as the acid becomes more dilute. Larger Percent dissociation for which one? 1.0 M HC2H3O2 or M HC2H3O2?
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HC9H7O4 C9H7O4- + H+ HANDOUT!!! DO ALL WORK ON THIS!!!
Aspirin, is a weak organic acid whose molecular formula is HC9H7O4. An aqueous solution of aspirin has a total volume of mL and contains 1.26 g of aspirin. The pH of the solution is found to be Calculate Ka for aspirin.culate the Ka for aspirin Step #1: Write the dissociation equation HC9H7O4 C9H7O4- + H+
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I C E HC9H7O4 C9H7O4- + H+ Step #2: Determine concentration of acid!
1.26 g x 1 mol .350L g = 0.02M HC9H7O4 Step #3: ICE it! HC9H7O4 C9H7O4- + H+ I C E .02 - x +x +x .02 - x x x
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HC9H7O4 C9H7O4- + H+ E Step #4: Determine the [H+] pH = 2.60
[H+] = 2.5 x 10-3 M Step #5: Set up the law of mass action HC9H7O4 C9H7O4- + H+ E .02 - x x x 2 x2 .0025 Ka = Ka = Ka = 3.6 x 10-4 .02 - x
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Dissociation of Strong Bases
MOH(s) M+(aq) + OH-(aq) Strong bases are metallic hydroxides Group I hydroxides (NaOH, KOH) are very soluble Group II hydroxides (Ca, Ba, Mg, Sr) are less soluble pH of strong bases is calculated directly from the concentration of the base in solution
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Reaction of Weak Bases with Water
The generic reaction for a base reacting with water, producing its conjugate acid and hydroxide ion: B + H2O BH+ + OH- (Yes, all weak bases do this – DO NOT endeavor to make this complicated!)
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Reaction of Weak Bases with Water
The base reacts with water, producing its conjugate acid and hydroxide ion: CH3NH2 + H2O CH3NH3+ + OH- Kb = 4.38 x 10-4
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Kb for Some Common Weak Bases
Many students struggle with identifying weak bases and their conjugate acids.What patterns do you see that may help you? Base Formula Conjugate Acid Kb Ammonia NH3 NH4+ 1.8 x 10-5 Methylamine CH3NH2 CH3NH3+ 4.38 x 10-4 Ethylamine C2H5NH2 C2H5NH3+ 5.6 x 10-4 Diethylamine (C2H5)2NH (C2H5)2NH2+ 1.3 x 10-3 Triethylamine (C2H5)3N (C2H5)3NH+ 4.0 x 10-4 Hydroxylamine HONH2 HONH3+ 1.1 x 10-8 Hydrazine H2NNH2 H2NNH3+ 3.0 x 10-6 Aniline C6H5NH2 C6H5NH3+ 3.8 x 10-10 Pyridine C5H5N C5H5NH+ 1.7 x 10-9
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A Weak Base Equilibrium Problem
What is the pH of a 0.50 M solution of ammonia, NH3, Kb = 1.8 x 10-5 ? Step #1: Write the equation for the reaction NH3 + H2O NH4+ + OH-
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A Weak Base Equilibrium Problem
What is the pH of a 0.50 M solution of ammonia, NH3, Kb = 1.8 x 10-5 ? Step #2: ICE it! NH3 + H2O NH4+ + OH- I C E 0.50 - x +x +x x x x
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A Weak Base Equilibrium Problem
What is the pH of a 0.50 M solution of ammonia, NH3, Kb = 1.8 x 10-5 ? Step #3: Set up the law of mass action NH3 + H2O NH4+ + OH- E x x x
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A Weak Base Equilibrium Problem
What is the pH of a 0.50 M solution of ammonia, NH3, Kb = 1.8 x 10-5 ? Step #4: Solve for x, which is also [OH-] NH3 + H2O NH4+ + OH- E x x x [OH-] = 3.0 x 10-3 M
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A Weak Base Equilibrium Problem
What is the pH of a 0.50 M solution of ammonia, NH3, Kb = 1.8 x 10-5 ? Step #5: Convert [OH-] to pH NH3 + H2O NH4+ + OH- E x x x
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ANOTHER TIP OF THE DAY Ka x Kb = Kw
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The calculation of concentration and pH for
weak acids is more complex than for strong acids due to: The incomplete ionization of weak acids. The low Ka value for strong acids. The more complex atomic structures of strong acids. D. The low percent ionization of strong acids. E. The inconsistent Kb value for strong acids. Answer: A Strong acids ionize 100%, therefore, the [H+] is equal to the initial concentration of the strong acid. This is not the case for weak acids. Since not all of the acid ionizes, it is necessary to determine both how much of the acid forms H+ and how much is left in molecular form.
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The general reaction of an acid dissolving
in water may be shown as HA (aq) + HOH (l) H3O (aq) + A-(aq) A conjugate acid base pair for this reaction is: HA and HOH HA and A- HOH and A- H3O+ and A- HA and H3O+ Answer: B The conjugate acid differs from its conjugate base by a proton, (H+). The acid form has the proton (HA in this example) and the base form has lost the proton (A- in this case).
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Strong acids are those which
Have an equilibrium lying far to the left. Yield a weak conjugate base when reacting with water Have a conjugate base which is a stronger base than water D. Readily remove the H+ ions from water. E. Are only slightly dissociated (ionized) at equilibrium. Answer: B Strong acids give up their protons (H+ ions) easily. If their conjugate base form were strong, then the acid formed would hold strongly to the H+, which would not be a characteristic of a strong acid.
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When calculating the pOH of a hydrofluoric acid solution
(Ka = 7.2 x 10-4) from its concentration, the contribution of water ionizing (Kw = 1.0 x 10-14) is usually ignored because Hydrofluoric acid is such a weak acid. Hydrofluoric acid can dissolve glass The ionization of water provides relatively few H+ ions. The [OH-] for pure water is unknown. The conjugate base of HF is such a strong base. Answer: C By comparing the Ka for HF with Kw (for water), you can see that even though hydrofluoric acid is a very weak acid it is a much stronger acid than is water, so much so that the H+ ion contribution of water may be ignored.
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The percent dissociation (percent ionization) for weak acids
Is always the same for a given acid, no matter what the concentration. B. Usually increases as the acid becomes more concentrated. C. Compares the amount of acid that has dissociated at equilibrium with the initial concentration of the acid. D. May only be used to express the dissociation of weak acids. E. Has no meaning for polyprotic acids. Answer: C the percent dissociation does change with the concentration of the acid.
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The [OH-] of a certain aqueous solution is 1.0 x 10-5M.
The pH of this same solution must be 1.0 x 10-14 5.00 7.00 9.00 12.00 Answer: D Referring to pH + pOH = at 25oC, if [OH-] = 1 x 10-5M, pOH = 5, pH = =9.0
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In many calculations for the pH of a weak acid from the
concentration of the acid, an assumption is made that often takes the form [HA]o – x = [HA]o This Is valid because x is very small compared to the initial concentration of the weak acid. B. Is valid because the concentration of the acid changes by such large amounts. C. Is valid because actual value of x cannot be known. D. Is valid because pH is not dependent upon the concentration of the weak acid. E. Approximation is always shown to be valid and so need not be checked. Answer: A. We can expect x to be very small (as indicated by the low value for Ka for weak acids), so that the concentration of the weak acid does not significantly change from its initial value. As the final step in such problems, you must determine that the change in the initial [HA] is less than 5% for the approximation to be considered valid.
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HA is a weak acid which is 4.0% dissociated at 0.100M.
Determine the Ka for this acid 0.0040 0.040 1.6 16.5 Answer: B [HA]o = 0.100M [H+] = [A-] = 0.004M Ka = [H+][A-]/[HA] = (0.004 x 0.004) / = (4 x 10-3)(4 x 10-3) / (10-1) = 1.6 x 10-4
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SALTS
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Acid-Base Properties of Salts
Type of Salt Examples Comment pH of solution Cation is from a strong base, anion from a strong acid KCl, KNO3 NaCl NaNO3 Both ions are neutral Neutral These salts simply dissociate in water: KCl(s) K+(aq) + Cl-(aq)
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Acid-Base Properties of Salts
Type of Salt Examples Comment pH of solution Cation is from a strong base, anion from a weak acid NaC2H3O2 KCN, NaF Cation is neutral, Anion is basic Basic The basic anion can accept a proton from water: C2H3O H2O HC2H3O2 + OH base acid acid base
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Acid-Base Properties of Salts
Type of Salt Examples Comment pH of solution Cation is the conjugate acid of a weak base, anion is from a strong acid NH4Cl, NH4NO3 Cation is acidic, Anion is neutral Acidic The acidic cation can act as a proton donor: NH4+(aq) NH3(aq) + H+(aq) Acid Conjugate Proton base
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Acid-Base Properties of Salts
Type of Salt Examples Comment pH of solution Cation is the conjugate acid of a weak base, anion is conjugate base of a weak acid NH4C2H3O2 NH4CN Cation is acidic, Anion is basic See below IF Ka for the acidic ion is greater than Kb for the basic ion, the solution is acidic IF Kb for the basic ion is greater than Ka for the acidic ion, the solution is basic IF Kb for the basic ion is equal to Ka for the acidic ion, the solution is neutral
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Acid-Base Properties of Salts
Type of Salt Examples Comment pH of solution Cation is a highly charged metal ion; Anion is from strong acid Al(NO3)2 FeCl3 Hydrated cation acts as an acid; Anion is neutral Acidic Step #1: AlCl3(s) + 6H2O Al(H2O)63+(aq) + Cl-(aq) Salt water Complex ion anion Step #2: Al(H2O)63+(aq) Al(OH)(H2O)52+(aq) + H+(aq) Acid Conjugate base Proton
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Summary of Acid/Base Properties of Salts:
Cation From Anion From Solution Strong Base Weak Base Strong Acid Weak Acid Neutral Basic Acidic Must compare K values!
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Effect of Structure on Acid-Base Properties
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Question: Do I really know this stuff?
Answer: Let’s find out! Good luck
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Let’s try this: Determine the pH of a 0.10M solution of NaC2H3O2. Ka for HC2H3O2 is 1.8 x 10-5 Good luck
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PRACTICE TIME! Please complete problems: #44,50,52, and 64a-d
on a separate sheet of paper (Will be collected at end of block!) You may work with other students AT YOUR WORKSTATION!
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PRACTICE TIME! pp. 673-75: #28,30,32,36,38,40,44,50 52 and 55.
PLEASE BEGIN TO SOLVE THE FOLLOWING PROBLEMS RELATING TO: NATURE OF ACIDS-n-BASES, AUTOIONIZATION OF WATER, pH SCALE AND THE SOLUTIONS OF ACIDS. pp : #28,30,32,36,38,40,44,50 52 and 55.
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Please complete problems: on a separate sheet of paper
PRACTICE TIME! Please complete problems: Pp 64a-d and # 78,82,84,86,92 and 94 on a separate sheet of paper
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PRACTICE TIME! Please complete problems: #44,50,52,58,59 and 64a-d
on a separate sheet of paper (Will be collected at end of block!)
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PRACTICE TIME! PLEASE BEGIN TO SOLVE THE FOLLOWING PROBLEMS RELATING TO: NATURE OF ACIDS-n-BASES, AUTOIONIZATION OF WATER, pH SCALE AND THE SOLUTIONS OF ACIDS. pp : #28-30,32,33-36,38,40,44,50 52,55,58,59, and 64a-d Please complete problems #28-30,32,33-36,38 and 40 on a separate sheet of paper (Will be collected at end of block!)
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PRACTICE TIME! pp : #78,82,84,86,92 and 94
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PRACTICE TIME! pp : # 43-46,50,52,55,58, 59,62 and 64(a-d)
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