Chem17 2 Sem 2010-2011: Goals Properties of Aqueous Solutions of Acids

Chem17 2nd Sem 2010-2011 Review of Concepts on Acids and Bases
GOALS
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Properties of Aqueous Solutions of Acids and Bases The Arrhenius Theory The Hydronium Ion (Hydrated Hydrogen Ion) The Brnsted-Lowry Theory The Autoionization of Water Amphoterism Strengths of Acids Acid-Base Reactions in Aqueous Solutions Acidic Salts and Basic Salts The Lewis Theory
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Properties of Aqueous Solutions of Acids

Aqueous acidic solutions have the following properties:
1. Have a sour taste. 2. Change the colors of many indicators. Acids turn blue litmus to red. Acids turn bromothymol blue from blue to yellow. 3. React with metals to generate hydrogen, H2(g). 4. React with metal oxides and hydroxides to form salts and water. 5. React with salts of weaker acids to form the weaker acid and the salt of the stronger acid.
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Do NOT Reproduce/Photocopy. Copyrighted!
Properties of Aqueous Solutions : Bases

Aqueous basic solutions have the following properties:
1. They have a bitter taste. 2. They have a slippery feeling. 3. They change the colors of many indicators Bases turn red litmus to blue. Bases turn bromothymol blue from yellow to blue. 4. They react with acids to form salts and water. 5. Aqueous basic solutions conduct electricity.
The Arrhenius Theory

Svante Augustus Arrhenius first presented this theory of acids and bases in 1884. Acids are substances that contain hydrogen and produce H+ in aqueous solutions. Two examples of substances that behave as Arrhenius acids:

Bases are substances that contain the hydroxyl, OH, group and produce hydroxide ions, OH-, in aqueous solutions. Examples of substances that behave as Arrhenius bases:
HCl(aq) + H 2O(l ) H 3O(+aq) + Cl(-aq ) + HCO 2H (aq) + H 2O( l ) H 3O ( + HCO 2(aq) aq )

NaOH Na (+aq ) + OH (-aq ) Ca(OH) Ca 2+ + 2 OH

2
(aq )
(aq )
6

Neutralization reactions are the combination of H+ (or H3O+) with OH- to form H2O. Strong acids are acidic substances that ionize 100% in water.
List of aqueous strong acids: HCl, HBr, HI, H2SO4, HNO3, HClO4, HClO3

For a typical strong acid-strong base reaction, the formula unit, total ionic, and net ionic equations are given below. The formula unit equation is:

What are the spectator ions in this reaction?
Cl (aq ) + Na (+aq )
The net ionic equation is:
H (+aq ) + OH ( aq ) H 2 O ( l)
HCl (aq ) + NaOH (aq ) NaCl(aq ) + H 2 O(l)

The total ionic equation is:
+ H (+aq ) + Cl (aq ) + Na (+aq ) + OH ( aq ) Na (aq ) + Cl (aq ) + H 2 O (l )
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Strong bases are basic substances that ionize 100% in water.

List of aqueous strong bases: LiOH, NaOH, KOH, RbOH, CsOH, Ca(OH)2, Sr(OH)2, Ba(OH)2
All strong acid-strong base reactions have this net ionic equation.
The Hydronium Ion (Hydrated Hydrogen Ion)

The protons that are generated in acid-base reactions are not present in solution by themselves. Protons are surrounded by several water molecules.
The number of molecules varies from solution to solution.
The Brnsted-Lowry Theory

J.N. Brnsted and T.M. Lowry developed a more general acid-base theory in 1923. An acid is a proton donor (H+). A base is a proton (H+) acceptor.

Acid-base reactions are the transfer of a proton from an acid to a base.
HCl + NH 3 NH + 4 + Cl
HBr + H 2 O H 3 O + + Br acid base NH 3 + H 2 O NH + 4 + OH base acid
acid
base
H+(aq) is really H(H2O)n+ where n is a small integer. Chemists normally write the hydrated hydrogen ion as H3O+ and call it the hydronium ion.
Note that coordinate covalent bonds are often made in these acid-base reactions.
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Reaction of Strong Acid with water (Ionization)

Conjugate acidacid-base pairs
An important part of Brnsted-Lowry acid-base theory is the idea of conjugate acid-base pairs.
Two species that differ by a proton are called acid-base conjugate pairs.

Conjugate acid-base pairs are species that differ by a proton.
Standard format for writing conjugate acid-base pairs.
For example: HNO3
+ H2O
H3O+
NO3-
HF + H 2 O H 3O + + F acid1 base 2 acid 2 base1 F- - base1

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HNO3 is the acid, conjugate base is NO3H2O is the base, conjugate acid is H3O+
HF - acid1
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The subscript 1' s indicate the 1st pair.

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The major differences between Arrhenius and Brnsted-Lowry theories. 1. The reaction does not have to occur in an aqueous solution. 2. Bases are not required to be hydroxides.

An important concept in Brnsted-Lowry theory involves the relative strengths of acid-base pairs. Weak acids have strong conjugate bases. Weak bases have strong conjugate acids. The weaker the acid or base, the stronger the conjugate partner.
The reason why a weak acid is weak is because the conjugate base is so strong it reforms the original acid. This reasoning could be applied for weak bases.

NH 3 + H 2O NH + 4 + OH
Since NH3 is a weak base, NH4+ must be a strong acid.

NH4+ gives up H+ to reform NH3.
Compare that to NaOH Na+ (aq) + OH-(aq)

Na+ must be a weak acid or it would recombine to form NaOH
Remember NaOH ionizes 100%.

NaOH is a strong base.
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Amines are weak bases that behave similarly to ammonia. The functional group for amines is an -NH2 group attached to other organic groups.
The Autoionization of Water

Water can be either an acid or base in Bronsted-Lowry theory. Consequently, water can react with itself. This reaction is called autoionization. One water molecule acts as a base and the other as an acid. + -
Self-ionization of water
H O H Base (1) Acid (2)
H H O H Acid (1) Base (2)

+
NH + + OH NH 3 + H 2 O 4 + CH 3 NH 2 + H 2 O CH 3 NH 3 + OH Do NOT Reproduce/Photocopy. Copyrighted! 19
H O + OH H 2O + H 2O 3 acid 2 acid1
base1
base2
H2O + H2O
H3O+ + OH-
Water does not do this extensively. [H3O+] = [OH-] 1.0 x 10-7 M Autoionization is the basis of the pH scale.
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Kw = [H3O+][OH-]
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Amphoterism
Some species can behave as both acids and bases. They are called amphoteric substances (also called ampholytes). Proton transfer reactions in which a species behaves as either an acid or base is called amphiprotic.
Amphoterism
Examples of amphoteric species are hydroxides of elements with intermediate electronegativity.
Example: Zn and Al hydroxides
Amphoterism
Molecular equation for the reaction of zinc hydroxide with nitric acid.
Zn(OH)2 + 2 HNO3 Zn(NO3 ) 2 + 2 H 2 O

What is the total ionic equation ?
Zn(OH) 2 + 2H + + 2 NO-3 Zn 2+ + 2 NO-3 + 2 H 2O
Zn(OH)2 behaves as a base in presence of strong acids.
Net ionic equation:
Zn(OH)2 + 2H + Zn 2+ + 2 H 2O
Amphoterism
Zn(OH)2 behaves as an acid in presence of strong bases. Molecular equation
Zn(OH)2 + 2KOH K2Zn(OH)4 Zn(OH)2 is insoluble until it reacts with KOH
Strengths of Acids (non-aqueous media)

For binary acids, acid strength increases with decreasing H-X bond strength. For example, the hydrohalic binary acids Bond strength has this periodic trend.
HF >> HCl > HBr > HI
Strengths of Acids
The same trend applies to the VIA hydrides. Their bond strength has this trend.
H2O >> H2S > H2Se > H2Te
What is the total ionic equation?

+ + 2Zn(OH) 2 + 2K + 2OH 2K + Zn(OH) 4
Acid strength has the reverse trend.

HF << HCl < HBr < HI CAUTION! However, take note of water leveling effect. In aqueous solutions, 10mL 1 M HI has the same acid strength as a 10 mL 1 M HCl.
The acid strength is the reverse trend.

H2O << H2S < H2Se < H2Te
Note: The above acid-base trend is true for both aqueous and non-aqueous solutions.
Zn(OH) 2 + 2 OH - Zn(OH) 2 4
Strengths of Acids:
Leveling effect
The acid leveling effect masks the differences in acid strength of the hydrohalic acids.
The strongest acid that can exist in water is H3O+.
Strengths of Acids
HBr, which should be a weaker acid, has the same strength in water as HI. HBr + H2O H3O+ + Bressentially 100% Acid strength differences for strong acids can only be distinguished in non-aqueous solutions like acetic acid, acetone, etc.
Strengths of Acids
Using our knowledge of Brnsted-Lowry theory, it is possible to construct a relative ranking of acid and base strengths (and their conjugate partners.)
Acids that are stronger than H3O+ merely react with water to produce H3O+. Consequently all strong soluble acids have the same strength in water. HI + H2O H3O+ + Iessentially 100%
Acid Strong Acid HClO4 H3O+ CH3COOH HCN H2O NH3

Conjugate Base Weak Base ClO4acid loses H+ H2O CH3COOCNOHNH230

base gains H+
Strengths of Acids
It is possible to do this for essentially every acid and base (and their partners).
Strengths of Acids
The strongest acid that can exist in water is H3O+. HCl + H2O H3O+ + Cl HCl is strong enough that it forces water to accept H+.
Strengths of Acids
Ternary acids are hydroxides of nonmetals that produce H3O+ in water.
Consist of H, O, and a nonmetal.
The strongest base that can exist in water is OH-. NH2- + H2O NH3 + OH NH2- is strong enough to remove H+ from water.
HClO4
H3PO4
The reason that stronger acids and bases cannot exist in water is that water is amphiprotic.
Strengths of Acids
HClO4 H3PO4
Strengths of Acids
It is a very common mistake for students to not realize that the Hs are attached to O atoms in ternary acids.
Although chemists write them as HClO4.
Strengths of Ternary Acids

Recall that for binary acids, acid strength increased with decreasing H-X bond strength. Ternary acids have the same periodic trend. Strong ternary acids have weaker H-O bonds than weak ternary acids. For example, compare acid strengths:
HNO2<HNO3 H2SO3< H2SO4
This implies that the H-O bond strength is: HNO2 > HNO3 H2SO3 > H2SO4
Strengths of Acids
Ternary acid strength usually increases with: 1. an increasing number of O atoms on the central atom 2. an increasing oxidation state of central atom. Effectively, these are the same phenomenon. Every additional O atom increases the oxidation state of the central atom by 2. For ternary acids having the same central atom:
the highest oxidation state of the central atom is usually strongest acid.
Acid-Base Reactions in Aqueous Solutions

There are four acid-base reaction combinations that are possible:
1. 2. 3. 4. Strong acids strong bases Weak acids strong bases Strong acids weak bases Weak acids weak bases
Acid-Base Reactions in Aqueous Solutions

1. Strong acids - strong bases
forming soluble salts hydrobromic acid + calcium hydroxide
This is one example of several possibilities The molecular equation is: 2 HBr(aq) + Ca(OH)2(aq) CaBr2(aq) + 2 H2O(l)
Consider the strength of the Cl ternary acids.

HClO < HClO2 < HClO3 < HClO4 weakest strongest
Cl oxidation states
+1
+3
+5
+7
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The Lewis Theory

Developed in 1923 by G.N. Lewis.
This is the most general of the present day acid-base theories. Emphasis on what the electrons are doing as opposed to what the protons are doing.
The Lewis Theory

One Lewis acid-base example is the ionization of ammonia.
+ NH 3 + H 2O NH 4 + OH -
The Lewis Theory

Look at this reaction in more detail paying attention to the electrons.
H
+
H H
Acids : electron pair acceptors. Bases : electron pair donors. Neutralization reactions are accompanied by coordinate covalent bond formation.
base acid
N
H H H
N
H H
O Acid - it accepts the electron pair
Base - it donates the electron pair
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Notice that a coordinate covalent bond is formed on the ammonium ion.
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The Lewis Theory

Ionization of HBr HBr + H2O H3O+ + Br acid base
The Lewis Theory: example

The autoionization of water.
The Lewis Theory

The reaction of sodium fluoride and boron trifluoride provides an example of a reaction that is ONLY a Lewis acid-base reaction.
It does not involve H+ at all; thus, it cannot be an Arrhenius nor a Brnsted-Lowry acid-base reaction.
Again, a more detailed examination keeping our focus on the electrons.

H
H O + + OH H 2O + H 2O 3
+
_
Br
H
acid
base
Br
+
H
O
H H
NaF + BF3 Na+ + BF4Do NOT Reproduce/Photocopy. Copyrighted! 44 Do NOT Reproduce/Photocopy. Copyrighted! 45
Acid - it accepts Base- it donates the electron pair the electron pair Do NOT Reproduce/Photocopy.
Copyrighted!
covalent coordinate bond formed 43
The Lewis Theory

NaF + BF3 Na+ + BF4_ F +
F F F
The Lewis Theory

F F
Acid Base Reaction

CH3NH3 (methylamine) reacts with water to form a hydroxide and a protonated methylamine.
H O -
BF3 is a strong Lewis acid.

The movie shows the Lewis acid BF3 reacting with NH3
B
F F
H H C H
H N H
H H C H
H N+ H
Base - it donates the electron pair
Acid - it accepts the electron pair
coordinate covalent bond formed

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Strengths of Oxoacids
Organic Acids

H O H O H H C H H C H O H H C H Acetic acid C
Focus on the Anions Formed

Ethoxide ion H H Acetate ion C H H C H H H O C H O
Ka = 1.810-5
H-O-Cl ENCl = 3.0 Ka = 2.910-8
Ka =1.310-16
C H
C O
H-O-Br ENBr= 2.8 Ka = 2.110-9

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Ethanol
Chain length has little effect:

H H C H H H C H H C H H C H O C O
but substitution may strongly affect acid strength:
Strengths of Amines as Bases

H H N H ammonia H
Ka = 1.810-5
C H
C H
C O
Ka = 1.810-5
Br
N H
Ka = 1.310-5
H C H H C H H C H
Ka = 1.410-3
Cl
bromamine pKa 7.61 pKb 6.39
C H
C O
C O
= pKb = 4.74
Electron Withdrawing Br
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Factors promoting electron withdrawal from the OH bond to the oxygen atom: High electronegativity (EN) of the central atom. A large number of terminal O atoms in the molecule.
Strengths of Amines as Bases

H H C H methylamine pKb = 4.74 NH2 H H C H H C H NH2 H H C H H C H H C H NH2
H H N H base
H F H N

B F
Electrons are delocalized, hence
Lewis acid A species (atom, ion or molecule) that is an electron pair acceptor. Lewis base A species that is an electron pair donor.
F F
Lewis Acids and Bases
ethylamine pKa = 3.38
propylamine pKb = 3.37
B F acid
More electrons to delocalize

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F H adduct
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Complex ions
Predicting acidity of metalhydrates: SIZE vs. CHARGE

Hydrolysis of small, highly-charged cations. They are ACIDIC.
Example: Dissolution of AlCl3(s) in water is exothermic due to formation of [Al(H2O)6]3+
Most of them have coordination six (octahedral).
FIGURE 16-11
TRENDS in ACIDITY Smaller, more charged cations are stronger acids than larger ones. For isoelectronic ions (Li+ vs. Be+2), the smaller one is more acidic (I.e. Be+2) For same element, different oxidation state, again, the more highly charged is the one easily hydrolyzable.
Fe+3 has a large Ka than Fe+2
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The Lewis structure of [Al(H2O)6]3+ and a ball-and-stick representation Do NOT Reproduce/Photocopy. Copyrighted! 58 Do NOT Reproduce/Photocopy. Copyrighted!
Small-cations: acidic in water

Which one is more acidic Al+3 or Mg+2? The ioniuc radii are 0.68A-Al vs. 0.85A-Zn Ka values: 1x10-5 Al vs. 3.0 x 10-12 The greater the charge on the cation, the greater is its ability to draw electron density away from the OH(of water); the smaller the cation, the more concentrated is the positive charge). Charge density = ionic charge/ionic volume. Such that Na+ is not acidic anymore (pKa 14.2) Do NOT Reproduce/Photocopy. compared to Al+3 (pKa 5.0) Copyrighted!
FIGURE 16-11
Hydrolysis of [Al(H2O)6]3+ to produce H3O+


Chem17 2 Sem 2010-2011: Goals Properties of Aqueous Solutions of Acids

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Chem17 2nd Sem 2010-2011 Review of Concepts on Acids and Bases

Properties of Aqueous Solutions of Acids

Do NOT Reproduce/Photocopy. Copyrighted!

Properties of Aqueous Solutions : Bases

The Arrhenius Theory

The Arrhenius Theory

HCl(aq) + H 2O(l ) H 3O(+aq) + Cl(-aq ) + HCO 2H (aq) + H 2O( l ) H 3O ( + HCO 2(aq) aq )

NaOH Na (+aq ) + OH (-aq ) Ca(OH) Ca 2+ + 2 OH

Do NOT Reproduce/Photocopy. Copyrighted!

The Arrhenius Theory

The Arrhenius Theory

The Arrhenius Theory

HCl (aq ) + NaOH (aq ) NaCl(aq ) + H 2 O(l)

Strong bases are basic substances that ionize 100% in water.

The Hydronium Ion (Hydrated Hydrogen Ion)

The Brnsted-Lowry Theory

The Brnsted-Lowry Theory

HBr + H 2 O H 3 O + + Br acid base NH 3 + H 2 O NH + 4 + OH base acid

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Do NOT Reproduce/Photocopy. Copyrighted!

Reaction of Strong Acid with water (Ionization)

The Brnsted-Lowry Theory

The Brnsted-Lowry Theory

Standard format for writing conjugate acid-base pairs.

For example: HNO3

HF + H 2 O H 3O + + F acid1 base 2 acid 2 base1 F- - base1

The subscript 1' s indicate the 1st pair.

The Brnsted-Lowry Theory

The Brnsted-Lowry Theory

The Brnsted-Lowry Theory

Since NH3 is a weak base, NH4+ must be a strong acid.

Compare that to NaOH Na+ (aq) + OH-(aq)

Remember NaOH ionizes 100%.

The Brnsted-Lowry Theory

The Autoionization of Water

H H O H Acid (1) Base (2)

NH + + OH NH 3 + H 2 O 4 + CH 3 NH 2 + H 2 O CH 3 NH 3 + OH Do NOT Reproduce/Photocopy. Copyrighted! 19

Zn(OH)2 + 2 HNO3 Zn(NO3 ) 2 + 2 H 2 O

Zn(OH)2 behaves as a base in presence of strong acids.

Net ionic equation:

Strengths of Acids (non-aqueous media)

What is the total ionic equation?

Acid strength has the reverse trend.

The acid strength is the reverse trend.

Acid Strong Acid HClO4 H3O+ CH3COOH HCN H2O NH3

Conjugate Base Weak Base ClO4acid loses H+ H2O CH3COOCNOHNH230

Strengths of Ternary Acids

Acid-Base Reactions in Aqueous Solutions

Acid-Base Reactions in Aqueous Solutions

Consider the strength of the Cl ternary acids.

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Do NOT Reproduce/Photocopy. Copyrighted!

The Lewis Theory

The Lewis Theory

The Lewis Theory

O Acid - it accepts the electron pair

Base - it donates the electron pair

Do NOT Reproduce/Photocopy. Copyrighted!

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Notice that a coordinate covalent bond is formed on the ammonium ion.

The Lewis Theory

The Lewis Theory: example

The Lewis Theory