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Acids and Bases Chapter 14

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1 Acids and Bases Chapter 14
DE Chemistry Dr. Walker

2 Acid – Base Terminology
Arrhenius Acids produce hydrogen ions in aqueous solutions Based produce hydroxide ions in aqueous solutions Bronsted-Lowry Acids are proton donors Bases are proton acceptors Lewis Acids are electron pair acceptors Bases are electron pair donors

3 Conjugate Acids and Bases
HCl + H2O Cl- + H3O+ Acid Base Conjugate Conjugate Base Acid Conjugate Base – Formed when acid loses a proton Conjugate Acid – Formed when base gains a

4 Acid Dissociation HA H A- Acid Proton Conjugate Base

5 Acid Dissociation HA H+ + A- Acid Proton Conjugate Base
-Based on equilbirium constants from last chapter -Ka is very high for strong acids, lower for weak acids

6 Dissociation of Strong Acids
Strong acids are assumed to dissociate completely in solution. Large Ka or small Ka? Reactant favored or product favored?

7 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 

8 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?

9 Strong and Weak Acids/Bases
Strong Acid – dissociates completely in solution -Notice the HCl completely breaks apart -Tends to be smaller molecules Weak Acid – dissociates partially in solution Notice the acetic acid stays mostly intact -Tends to be larger, organic molecules

10 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  Lower Ka = less dissociation = weaker acid!!!

11 Acid Terminology Polyprotic – Acids with more than one ionizable proton Monoprotic - one acidic proton (HCl) Diprotic - two acidic protons (H2SO4) Triprotic - three acidic protons (H3PO4) Oxyacids - acids in which the acidic proton is attached to an oxygen atom (HClO3) Ionizable Hydrogen

12 Polyprotic Acids When multiple acidic protons are present, the removal of each one gives a different equilibrium constant The first one will always have the highest (strongest) equilibrium constant

13 Acid Terminology Organic acids - acids containing the mildly acidic carboxyl group Generally weak acids Equilibrium lies far to the left (weak acids)

14 Self-Ionization of Water
H2O + H2O H3O+ + OH- This happens in every glass of water This occurs in low enough concentration that it is not noticeable [H3O+] = [OH-] = 1.0 x 10-7 M [H3O+] [OH-] = 1.0 x M

15 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

16 Calculating pH, pOH pH = -log[H3O+] pOH = -log[OH-] Relationship between pH and pOH pH + pOH = 14 Finding [H3O+], [OH-] from pH, pOH [H3O+] = 10-pH [OH-] = 10-pOH

17 The pH scale – Examples of everyday items

18 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+

19 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

20 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 For weak acids, dissociation is small enough that It is assumed that a weak acid (acetic acid, here), dissociates less than 5%

21 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

22 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

23 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

24 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 

25 A Weak Base Equilibrium Problem
What is the pH of a 0.10 M solution of ammonia, NH3, Kb = 1.8 x 10-5 ? Step #1: Write the equation for the reaction NH3 + H2O  NH4+ + OH-

26 A Weak Base Equilibrium Problem
What is the pH of a 0.10 M solution of ammonia, NH3, Kb = 1.8 x 10-5 ? Step #2: ICE it! NH3 + H2O  NH4+ + OH- I C E 0.10 - x +x +x x x x

27 A Weak Base Equilibrium Problem
What is the pH of a 0.10 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

28 A Weak Base Equilibrium Problem
What is the pH of a 0.10 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-] = 1.3 x 10-3 M

29 A Weak Base Equilibrium Problem
What is the pH of a 0.10 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

30 Effect of Structure on Acid-Base Properties
Hypochlorous acid Chlorous acid Chloric acid Perchloric acid Increasing Acidity (more oxygens)

31 Acid-Base Properties of Oxides
Acidic Oxides (also called acid anhydrides) Nonmetal oxides that react with water to form acidic solutions SO3(g) + H2O(l) H2SO4(aq) 2 NO2(g) + H2O(l) HNO3(aq) + HNO2(aq)

32 Acid-Base Properties of Oxides
Basic Oxides (also called basic anhydrides) Metallic oxides of Group 1A and 2A metals react with water to form basic solutions K2O(s) + H2O(l) KOH (aq) CaO(s) + H2O(l) Ca(OH)2(aq)

33 Titrations Type of quantitative analysis
Start with known concentration and volume of a solution, known as a titrant Titrant can be acid or base Add to a sample solution with unknown concentration, known as an analyte Analyte will be the opposite of the titrant Reaches the endpoint when the indicator turns color Indicator: Dye that changes color with a change in pH

34 A Titration Pictured Left: student performing a titration. The titrant is in a long tube called a buret. The analyte is in the Erlenmeyer flask below. Right: A close-up view of a buret, measuring in 0.1 mL increments.

35 Common Indicators

36 Calculations The most common calculation involves using dilutions
Example: mL of 0.1 M HCl solution is required to titrate 100 mL of a base. What is the concentration of the base?

37 Calculations The most common calculation involves using dilutions
Example: mL of 0.1 M HCl solution is required to titrate 50 mL of a base. What is the concentration of the base? M1V1 = M2V2 (0.1 M)(32.5 mL) = M2 (50 mL) M2 = M

38 Titration Curves Titration curves depict the change in pH versus the amount of titrant (acid or base) added

39 Additional Vocabulary
Equivalence Point – pH where the moles (acid) = moles (base) Notice the equivalence point depends on the strength of the acid being titrated

40 Titration Curves Notice the difference between the curves
Left: The titration of a strong acid has a sharp curve before reaching the equivalence point Right: The titration of the weak acid has a shallow curve prior to the equivalence point

41 Polyprotic Acids Polyprotic acids have multiple Ka values – one for each ionizable proton Each ionizable proton has a separate equivalence point at a different pH


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