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CHEM 1101: CHEMISTRY

(EEE/CoE)

LECTURE 8

ACIDS AND BASES Properties of Acids


taste sour (don't taste them!)... the word 'acid' comes from the Latin acere, which means 'sour' acids change litmus (a blue vegetable dye) from blue to red their aqueous (water) solutions conduct electric current (are electrolytes) react with bases to form salts and water evolve hydrogen gas (H2) upon reaction with an active metal (such as alkali metals, alkaline earth metals, zinc, aluminum)

Properties of Bases

taste bitter (don't taste them!) feel slippery or soapy (don't arbitrarily touch them!) bases don't change the color of litmus; they can turn red (acidified) litmus back to blue their aqueous (water) solutions conduct and electric current (are electrolytes) react with acids to form salts and water

Examples of Common Acids


citric acid (from certain fruits and veggies, notably citrus fruits) ascorbic acid (vitamin C, as from certain fruits) vinegar (5% acetic acid) carbonic acid (for carbonation of soft drinks) lactic acid (in buttermilk) Mineral acids like HCl, HNO3, H2SO4 etc

Examples of Common Bases


Caustic soda or lye (NaOH) Caustic potash (KOH) household ammonia (aqueous) [NH3]

BASE VS ALKALI Bases: Bases are metal oxides, hydroxides or compounds (such as NH3) that give OHions in aqueous solution. CuO (s) + 2HCl (aq.) CuCl2 (aq.) + H2O (l) NaOH (s) + HCl (aq.) NaCl (aq.) + H2O (l) H+ + OH- H2O NH3 (g) + H2O (l) NH4+ (aq.) + OH-

Acids and Bases (Updated on May 15, 2011)

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CHEM 1101: CHEMISTRY

(EEE/CoE)

LECTURE 8

Alkali: A base that dissolves in H2O to give OH- ions is called an alkali. NH3, NaOH are examples. All alkali are base, but all bases are not alkali. Strong and Weak Acids and Bases Strong Acids A strong acid is an acid which is fully ionised in solution. Strong acids are so fully ionised in solution (close to 100%, but not quite) that the equilibrium constant has very large values much greater than one million. e.g. HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq) Greater than 99.99% ionised

There aren't very many strong acids, which makes life very easy for you. Strong Acids The Formulae Sulphuric acid Hydrochloric acid Hybrobromic acid Hydroiodic acid Nitric acid Perchloric acid H2SO4 HCl HBr HI HNO3 HClO4

Weak Acids A weak acid is an acid which is only partially ionised in solution. This also means that it has a small value for the equilibrium constant for the ionisation reaction. The value tends to be less than one, and quite a lot less than one. e.g. CH3COOH(aq) + H2O(l) Strong Bases Similarly, a strong base is one which is fully ionised in solution. It also has a high value for the equilibrium constant for ionisation. Again there are not many of them, and again you can memorise them all.
Acids and Bases (Updated on May 15, 2011) Page 2

H3O+(aq) + CH3COO-(aq) Less than 0.4% ionised.

CHEM 1101: CHEMISTRY

(EEE/CoE)

LECTURE 8

Strong Bases The Formulae Lithium hydroxide Sodium hydroxide Potassium hydroxide Rubidium hydroxide Caesium hydroxide Barium hydroxide Calcium hydroxide Strontium hydroxide LiOH NaOH KOH RbOH CsOH Ba(OH)2 Ca(OH)2 Sr(OH)2

Weak Bases Again, anything else is automatically a weak base. As before, this means that they have a small value for the equilibrium constant for ionisation. Again, there is no reference to the concentration of the solution, or how corrosive it is. ================================================================== Three concept of acids and bases are: (1) Arrhenius concept (2) Bronsted-Lowry concept (3) Lewis concept Arrhenius concept (1884): An acid is a compound that releases H+ ions in H2O. A base is a compound that releases OH- ions in H2O. HCl + H2O H3O+ + ClNaOH + H2O Na+ + OHUsefulness: This concept is useful in the study of chemical reactions. Limitations: (a) Free H+ and OH- ions do not exist in water.
Acids and Bases (Updated on May 15, 2011) Page 3

CHEM 1101: CHEMISTRY

(EEE/CoE)

LECTURE 8

.. O: H

+ H

.. O H

+ H or H3O+

Hydronium ion

(b) Limited to water only. These definitions are applicable to water only. (c) Some bases do not contain OH-. Example: NH3, CaO Bronsted-Lowry concept (1923): An acid is any molecule or ion that can donate a proton (H+). A base is any molecule or ion that can accept a proton (H+).
+ H ACID .. N H base acid BASE H H + H Cl H N H H + or Cl-

CaO

O H

Ca(OH)2

base

acid

Bronsted-Lowry concept is superior to Arrhenius concept: (a) Much wider scope. (b) Not limited to aqueous solutions. NH3 + HCl NH4+ + Cl-

(c) Release of OH- not necessary to qualify as a base. NH3 + H+ base NH4+ acid

An acid is a proton donor, while a base is a proton acceptor. Conjugate acid and base:
Acids and Bases (Updated on May 15, 2011) Page 4

CHEM 1101: CHEMISTRY

(EEE/CoE)

LECTURE 8

In acid-base reaction the acid gives up its proton and produces a new base.
Conjugate pair HA acid + Bbase HB Conjugate acid Conjugate pair + AConjugate base

The new base (A-) that is related to the original acid (HA) is called a conjugate base. Similarly, the original base (B-) after a accepting a proton becomes a new acid is called a conjugate acid. Conjugate pair: The acid-base pairs associated with the loss or gain of proton is a called conjugates pair. In any acid-base reaction, there are two conjugate acid-base pairs. For example, HA and A-, HB and B-.
H+ H+ HCl acid NH4+ Conj. acid H+ H+ ClConj. base

NH3 base

A weak acid has a strong conjugate base. A weak base has a strong conjugate acid.
Conjugate pair CH3COOH weak acid + H2O weak base H3O+ stronger acid + CH3COOstronger base

Conjugate pair

A strong acid has a weak conjugate base. A strong base has a weak conjugate acid.
Acids and Bases (Updated on May 15, 2011) Page 5

CHEM 1101: CHEMISTRY

(EEE/CoE)

LECTURE 8

Conjugate pair HCl strong acid + H2O strong base H3O+ weak acid + Ciweak base

Conjugate pair

Conjugate acid and base of H2O and HCO3-:


-H+ H2O +H+ H3O+ conjugate acid of H2O CO3-2 conjugate base of HCO3OHconjugate base of H2O

-H+ HCO3+H+

H2CO3

conjugate acid of HCO3-

Classes of Bronsted Acids and Bases: Bronsted acids: (1) Monoprotic acids- donate one proton HF H+ + F-, CH3COOH CH3COO- + H+ (2) Polyprotic acids-donate two or more protons H2S 2H+ + S2-, C2O4H2 C2O42- + 2H+ Bronsted bases: (1) Monoprotic bases- accept one proton HS- + H+ H2S, H2O + H+ H3O+ (2) Polyprotic bases- accept two or more protons SO42- + 2H+ H2SO4, PO43- + 3H+ H3PO4+ Amphiprotic substances: Molecule or ions that behave both as Bronsted acid and base. For example, H2O.
HCl acid NH3 base + + H2O base H2O acid NH4+ + OHH3O+ + Cl-

Lewis concept (1930):


Acids and Bases (Updated on May 15, 2011) Page 6

CHEM 1101: CHEMISTRY

(EEE/CoE)

LECTURE 8

An acid is an electron-pair acceptor. A base is an electron-pair donor.

A Lewis acid

:B Lewis base

Complex

The combination of Lewis acid and Lewis base is called a complex. All cations or molecules short of an electron pair act as Lewis acids; and all anions or molecules having a lone pair of electron act as Lewis bases. Examples: (a)
H+ + H Lewis acid Lewis base .. N H .. :O .. H + :N H H F .. O .. F B F Complex H H H N H H

(b)

H+ F

H H N H H

(c)

B F

Factors that are responsible for the strength of acids and bases (1) Base Qualitative strength LiOH +1 Weak base NaOH +1 Strong base KOH +1 Very strong base CsOH +1 Strongest base Mg(OH)2 +2 Weaker base Weaker base Al(OH)3 0.50 +3 (amphoteric) (2) Ionization constant: The smaller the value of ionization constant (K), the less is the degree of ionization and hence less strong the acids (or bases). Charge of ion H3PO4 H+ + H2PO4 1

Size of metal ions: Size of metal ion () 0.60 0.95 1.33 1.69 0.65

Acids and Bases (Updated on May 15, 2011)

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CHEM 1101: CHEMISTRY

(EEE/CoE)

LECTURE 8

[ H + ][ H 2 PO 4 ] K= = 0.75 10-2 [ H 3 PO 4 ]
(3) Oxidation number: The oxidation number of the central atom determines the strengths of the acids.

H 2 SO 4 > H 3 PO4 > H 2 SO3


HClO4 > H 2 SO 4 > HNO3 > H 2 SO3 > H 3 AsO3 > HClO Note: S with oxidation number +6 in H2SO4 exerts a greater pull on all the electron pairs of O atoms than does S in H2SO3. (4) Ionic potential: The ratio between the charge and the radius of an ion is called ionic potential ( ). i.e. =
z ; where z is charge and r is radius. r
+7

+6

+5

+4

+6

+5

+4

+3

+1

> 3.2 < 2.3 2.3 < < 3.2

-acidic -basic -amphoteric (both acidic & basic)

(5) Electro negativity: The decreasing electro-negativity gives rise to decreasing strengths of acids in the order. F>O>N , HF > H2O > NH3

Decreasing the atomic size of halogens decreasing strengths of halogens acids (ii). Increasing bond length, decreasing bond energy, easily gives up proton. Bond distance of HI (1.7) is greater than HF(1.0). HI > HBr > HCl > HF (6) Number of oxygen and hydrogen atoms: The greater the difference between the number of oxygen and number of hydrogen atoms, the stronger the acid. H2SO4 > H2SO3, HNO3 > HNO2 (7) Number of non-hydrogenated oxygen molecule: The greater the number of non-hydrogenated O atoms per molecule, the greater is the strength of acid.

Acids and Bases (Updated on May 15, 2011)

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