1. Acids and Bases Acid-Base chemistry important in our everyday lives
acidity of our blood is carefully controlled
making sulfuric acid is an important industry
sulfuric acid is needed to make fertilizers, polymers, steel, etc.
environmental impact of acid rain

2. Acids and Bases Properties of acids taste sour
e.g. vinegar, citric acid in soda and candies
react with many metals (to form the metal ion and hydrogen gas
2H+ + Zn --> H2 + Zn+2
react with carbonates (to form CO2)
2H+ + CaCO3 --> Ca+2 + H2O + CO2

3. Acids and Bases
Properties of bases
bitter taste
slippery feel

4. Acids and Bases Definitions of Acids
Arrhenius - an acid produces H+ in aqueous solutions
Bronsted-Lowry - an acid is an H+ donor
Lewis - e- pair acceptor

5. Acids and Bases Definitions of Bases
Arrhenius - a base produces hydroxide ions in solution
Bronsted-Lowry - a base is an H+ acceptor
Lewis - a base is an e- pair donor

6. Acids and Bases Acid-Base Definitions
Arrhenius definition is limited to aqueous solutions, and only allows for one kind of base, those with hydroxide ions.
Bronsted-Lowry is a more general definitions, water can now act as a base.
Lewis - the most general definition

7. Acids and Bases Terms to know: proton - H+ ion
hydronium ion - H3O+; results from water reacting with H+
H2O + H+ --> H3O+
conjugate base - whatever is left from an acid after a proton has been donated
conjugate acid - whatever has been formed when a proton has been accepted by a base

8. Acids and Bases Acid Dissociation Constant
an equilibrium constant for the ionization or dissociation of an acid Ka
for HA(aq) + H2O(l) <==> H3O+(aq) + A-(aq)
Ka = [H3O+][A-] / [HA] which is equivalent to
Ka = [H+][A-] / [HA]
remember, pure liquids, like water, are not included in the equilibrium expression

9. Acids and Bases Acid Strength
defined by the equilibrium position of the dissociation reaction
Strong Acid - equilibrium lies far to the right, i.e. the acid is 100% ionized
the conjugate base of a strong acid is a much weaker base than water, i.e. the conjugate base will not accept the H+
the stronger the acid the weaker the conjugate base

10. Acids and Bases Weak acid not 100% ionized
equilibrium lies to the left
very little HA is ionized
the conjugate base of a weak acid is a stronger base than water, the conjugate base is more likely to accept an H+ than water
the weaker the acid, the stronger the conjugate base

11. Acids and Bases
The Six Strong Acids
HCl
H2SO4
HNO3
HBr HI
HClO4

12. Acids and Bases Oxyacids Organic acids Most acids are oxyacids
The acidic proton is attached to an oxygen atom
Organic acids
Generally weak acids
Contain the -COOH (carboxyl) group
ex: CH3COOH - acetic acid

13. Acids and Bases Water The most common amphoteric substance
water can act as both an acid and a base
water can autoionize:
H2O + H2O <==> H3O+ + OH-
one water molecule acts as an acid (H+ donor), the other acts as an acid (an H+ acceptor)
Kw = [H3O+][OH-] = 1.00 x @ 25oC
dissociation or ion product constant for water

14. Acids and Bases Kw
In any aqueous solution at 25oC, the product of [H+] and [OH-] will be 1.0 x 10-14
So if you know the [H+], you can figure out the [OH-] and vice versa
If [H+] = [OH-], the solution is neutral
If [H+] > [OH-], the solution is acidic
If [H+] < [OH-], the solution is basic

15. Acids and Bases pH scale
Because the [H+] in any solution is generally quite small, it is easier to use the pH scale to represent a solution’s acidity.
pH comes from the Danish…potenz or strength of the H+ ion
pH = - log[H+]
pOH = - log [OH-]

16. Acids and Bases pH is a log scale
when the pH changes by one, the [H+] concentration changes by a power of 10.
A solution with a pH of 3 has 10 times more H+ than a solution with a pH of 4, and 100 times more H+ than a solution with a pH of 5.
As pH decreases, the [H+] increases.
Rule for significant figures for logarithms - the number of places after the decimal point is equal to the number of significant figures in the original number
pH = - log 1.0 x 10-9 M (2 significant figures in 1.0 x 10-9)
pH = 9.00 ( 2 places after the decimal point for significant figures)

17. Acids and Bases Acid-Base Equilibria…or doing acid-base problems
the aqueous solutions contain many components
you must be able to determine which components are most significant and which can be ignored
you must be able to determine which reaction is most important of all the possible reactions

18. Acids and Bases Ex: Calculate the pH of 1.0 M HCl
First: Determine the major species
HCl is a strong acid, 100% ionized
Major species then will be H+, Cl- and H2O
Since this is an acidic solution with “lots” of H+, the [OH-] will be insignificant.
What about H2O <==> H+ + OH- ? Will any H+ come from this reaction?
Le Chatelier’s principle tells us that the reverse reaction will be favored because of the high concentration of H+ from the HCl, so we can ignore this reaction as a source of H+.
Thus the pH = - log (1.0) = 0.00

19. Acids and Bases pH of Weak Acid Solutions Calculate the pH of 1.0 M HF
Determine the major species: HF (because it is a weak acid, very little of it ionizes), and H2O
Which of these major species will provide the H+ ions?
Consider the Ka and Kw

20. Acids and Bases HF <==> H+ + F- Ka = 7.2 x 10-4
H2O <==> H+ + OH- Kw = 1.0 x 10-14
Because the Ka of HF is greater than the Kw, HF is a stronger acid than H2O, and will be the primary contributor of H+ in solution.
Use the Ka for HF to determine the [H+] at equilibrium, and then determine the pH.

21. Acids and Bases Simplifying acid-base equilibrium calculations
If Ka is small, then “x” is small relative to the original concentrations.
x becomes essentially 1.00 in these calculations
Is this a valid assumption? Please check at the end!
Compare x to [HAo], if x < 5% of [HAo], then the assumption is valid

22. Acids and Bases The pH of a mixture of weak acids
Calculate the pH of a solution that contains 1.00 M HCN (Ka = 6.2 x 10-10), and 5.00 M HNO2 (Ka = 4.0 x 10-4).
Determine the major species: HCN, HNO2, and H2O
Compare Ka’s and Kw.
The Ka for HNO2 is larger than Kw and the Ka for HCN
HNO2 <==> H+ + NO2- is the reaction of interest.

23. Acids and Bases % dissociation or % ionization
gives us an idea of the amount of weak acid that has dissociated
% dissociation = ([H+] /[HAo]) x 100
For a weak acid, the % ionization increases as the concentration gets more dilute.

24. Acids and Bases Bases Strong Bases
100% ionized
Group I hydroxides (e.g. NaOH, KOH, etc)
heavy Group II hydroxides (Ca(OH)2, Ba(OH)2, Sr(OH)2)
A base does not have to contain OH- ion to be a base

25. Acids and Bases Bases Ammonia: NH3 + H2O <==> NH4+ + OH-
The [OH-] increases due to the reaction of ammonia with water, so ammonia is a base, specifically, a Bronsted-Lowry base, because it is a proton acceptor.
Many bases are like ammonia with a lone pair of electrons on the nitrogen that can accept H+. Consider these bases as substituted ammonia molecules
e.g. CH3NH2, (CH3)2NH, (CH3)3N, C2H5NH2

26. Acids and Bases General reaction between a base and water
B + H2O <==> BH+ + OH-
Kb = [BH+][OH-]/[B]
In equilibrium problems involving weak bases, if Kb < Kw, then the base will be the primary source of OH-.

27. Acids and Bases Polyprotic Acids (many proton acids)
Some acids can donate more than one H+
e.g. H2SO4 and H3PO4
Polyprotic acids lose 1 H+ at a time.
H2SO4--> H+ + HSO Ka1 >> 0
HSO4- <==> H+ + SO4-2 Ka2 = 1.2 x 10-2
The decreasing Ka as protons are lost indicate it is less favorable (as the negative charge on the acid increases) to lose the second (or third) proton

28. Acids and Bases Acid-Base Properties of Salts Salt = an ionic compound
salts dissolve in water to form ions
sometimes these ions can react with water to form weak acids or weak bases

29. Acids and Bases Neutral Salts
When these salts dissolve in water, the pH does not change.
There is no reaction of the ions from the salt with water.
The anion and cation are derived from a strong acid and a strong base, respectively.

30. Acids and Bases
Ex. NaCl is a neutral salt. Na+, the cation, can be considered as coming from NaOH, a strong base. Cl-, , the anion, can be considered as coming from HCl, a strong acid. Remember the conjugates of strong acids and strong bases are very weak, weaker than water, and so are unlikely to react with water to reform the acid or base.

31. Acids and Bases
Na+ + H2O cannot form NaOH + H+…strong bases do not re-form in solution.
Cl- + H2O cannot HCl + OH- …strong acids do not re-form in solution.

32. Acids and Bases Basic Salts
The anion from this salt will react with water to form a weak acid and OH-.
The anion must have come from a weak acid originally.
Ex: NaCH3COO. The Na+ comes from a strong base, NaOH. CH3COO- comes from a weak acid, CH3COOH.
Na+ + H2O cannot form NaOH + H+
CH3COO- + H2O <==> CH3COOH + OH-

33. Acids and Bases Acidic Salts
The cation from an acidic salt will react with water to form a weak base and H+.
The cation must have come from a weak base.
Ex: NH4Cl. The NH4+ comes from a weak base, and will react with water to re-form the weak base and H+ (H3O+). The Cl- comes from a strong acid, and cannot react with water to re-form HCl.
NH4+ + H2O <==> NH3 + H3O+

34. Acids and Bases
How do we know the Kb for the conjugate base of a weak acid? How do we know the Ka for the conjugate acid of a weak base?
CH3COOH + H2O <==> CH3COO- + OH- Ka = 1.8 x 10-5
CH3COO- + H2O <==> CH3COOH + OH-
Kb = [CH3COOH][OH-]/[CH3COO-] = ?
Ka. Kb = Kw

35. Acids and Bases
Salts that are derived from both a weak acid and a weak base
We can predict whether the solution will be acidic or basic based on the Ka of the acidic ion and the Kb of the basic ion.
Ka > Kb pH < 7, acidic solution
Kb > Ka pH > 7, basic solution
Kb = Ka pH = 7, neutral solution

36. Acids and Bases The effect of structure on acid-base properties
Any molecule containing hydrogen could theoretically act as an acid. However, most of these molecules don’t.
Organic molecules with lots of C-H bonds are not acidic because the C-H is both strong, and relatively nonpolar, so there is no tendency to lose H+
However, while the H-Cl bond is stronger than the C-H bond, the H-Cl bond is very polar, and there is a strong tendency to lose H+.

37. Acids and Bases
Two Factors that determine the acidity of a molecule containing X-H
strength of the X-H bond
polarity of the X-H bond
Consider polarity of the X-H bond
H-F > H-Cl > HBr > HI in terms of polarity
H-F > H-Cl > H-Br > HI in terms of bond strength
HF is a weak acid, HCl, HBr, and HI are strong acids
even though the H-F bond is very polar, the H-F bond is very strong, so HF is a weak acid

38. Acids and Bases Oxyacids contains the grouping H-O-X
HClO4 Ka >>> 0
HClO3 Ka = 1
HClO2 Ka = 1.2 x 10-2
HClO Ka = 3.5 x 10-8
As the number of oxygen atoms increase, the acid strength increases

39. Acids and Bases
Oxygen is very electrognegative. With increasing number of oxygen atoms, the oxygen atom draw more and more of the electron density towards themselves, thus polarizing and weakening the O-H bond,

40. Acids and Bases This behavior also occurs with hydrated metal ions.
Al+3 is strongly attracted to water, weakening the O-H bond. The greater the charge on the metal ion, the stronger the acidity.

41. Acids and Bases
The greater the electronegativity of X in the H-O-X grouping, the stronger the acid.
X is able to withdraw electron density from the H-O bond, thus weakening and polarizing the H-O bond, resulting in a stronger acid

42. Acids and Bases
Comparison of Electronegativity of X and Ka

43. Acids and Bases Acid-Base Properties of Oxides
An H-O-X grouping in a molecule may result in a molecule that behaves as a base or an acid.
The nature of the O-X bond will determine the acidic or basic behavior of the molecule

44. Acids and Bases
If X is very electronegative, the O - X bond will be covalent (not as polar because of similar E.N.’s), and strong. The O - X bond will remain intact in water, while the polar and weak H - O bond will break, resulting in acidic behavior.
e.g. HClO2 or H2SO4
If X is not very electronegative, the O - X bond will be ionic, and can be broken in water, resulting in basic behavior.
e.g. NaOH or KOH

45. Acids and Bases Basically… Nonmetal oxides will form acids in water
SO2 + H2O <==> H2SO3
CO2 + H2O <==> H2CO3
Metal oxides will form bases in water
Na2O + H2O --> 2 NaOH
CaO + H2O --> Ca(OH)2
(the oxide ion has a high affinity for protons and reacts with water to form hydroxide ions)

46. Acids and Bases
Lewis acids and bases are electron pair acceptors and electron pair donors, respectively
A very general model for acids-base reactions…see Lewis structures for explanations...