Sie sind auf Seite 1von 12

1.

Acid-Base Theories
1.1.1.
Arrhenius Acids and Bases
In 1887, according to Swedish chemist Svante
Arrhenius, acids are compounds containing hydrogen
that ionize to produce hydrogen ions (H+) in aqueous
solution. On the other hand, bases are compounds that
ionize to produce hydroxide ions (OH-) in aqueous
solution.
1.1.2.
Brnsted-Lowry Acids and Bases
In 1923, Danish chemist Johannes Brnsted (18791947), and English chemist Thomas Lowry (1874-1936)
independently proposed a new theory. Brnsted-Lowry
acid is defined as a hydrogen-ion donor, and a
Brnsted-Lowry base is defined as a hydrogen-ion
acceptor.
1.1.3.
Lewis Acids and Bases
The third theory was proposed by Gilbert Lewis
(1875-1946). He focused on the donation or acceptance
of a pair of electrons during a reaction. A Lewis acid
is a substance that can accept a pair of electrons to
form covalent bond. A Lewis base is a substance that
can donate a pair of electrons to form covalent bond.

Type
Arrhenius
Brnsted-Lowry
Lewis

Table 1. Acid-Base Definitions


Acid
Base
+
H producer
OH producer
H+ donor
H+ acceptor
Electron-pair
Electron-pair
acceptor
donor

2. Arrhenius
Arrhenius acids are compounds that contain hydrogen that
ionize to yield hydrogen (H+) ions in aqueous solution.
Monoprotic acid is an acid that contains one ionizable
hydrogen. Nitric acid (HNO3) is an example. Sulfuric acid
(H2SO4) or any acid that contains two ionizable protons is
called diprotic acid. A tripotic acid is an acid that
contains three ionizable protons like in phosphoric acid
(H3PO4).
However, not all compounds containing hydrogen are acids
or hydrogens in an acid are released as hydrogen ions. Only
hydrogens in very polar bonds are ionizable.

Excemptions are made to methane (CH4) because the four


hydrogens are in weakly C-H bonds. Aside from that,
ethanoic acid (CH3COOH) is a monoprotic acid though it
contains four hydrogens.
H

I
II
H-C-C-O-H
I
H

ethanoic acid (C CH3COOH)

The structural formula shows that the three hydrogens are


in weakly polar bonds.
Table 2. Some
Name
Hydrochloric acid
Nitric acid
Sulfuric acid
Phosphoric acid
Ethanoic acid
Carbonic acid

Common Acids
Formula
HCl
HNO3
H2SO4
H3PO4
CH3COOH
H2Co3

Arrhenius bases are compounds that ionize to yield


hydroxide ions (OH-) in aqueous solution.
Table 3. Some Common Bases
Name
Formula Solubility in
water
Potassium
KOH
High
hydroxide
Sodium hydroxide
NaOH
High
Calcium hydroxide
Ca(OH)2 Very low
Magnesium
Mg(OH)2 Very low
hydroxide
Both potassium hydroxide and sodium hydroxide are ionic
solids. They dissociate completely into the metal ions and
hydroxide ions when dissolved in water. Elements in Group
1A (alkali metals), such as sodium and potassium, react
with water to produce alkaline solutions. Calcium hydroxide
[Ca(OH)2], and magnesium hydroxide [Mg(OH)2], are both
hydroxides of Group 2A metals. They are not very soluble in
water. Thus, their solutions are always very dilute, even
when saturated. The concentration of hydroxide ions in such
solutions is very low.

3. Brnsted-Lowry
A Bronsted-Lowry acid is defined as a hydrogen-ion donor,
while a Bronsted-Lowry base is a hydrogen-ion acceptor.
Lets have ammonia as an example. When ammonia dissolves
in water it acts as a base because it accepts a hydrogen
ion from water.
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)
In this reaction, ammonia is the Bronsted-Lowry base.
Water, on the other hand, is the Bronsted-Lowry acid.
Hydrogen ions are transferred from water to ammonia.
Heating an aqueous solution of ammonia drives off
ammonia gas. As the ammonia gas moves out of solution,
the equilibrium in the ammonia dissolution equation moves
to the left. The ammonium ion (NH4+) reacts with OH- to
form NH3 and H2O. When the reaction goes from right to
left, NH4+ gives up a hydrogen ion; it acts as a BronstedLowry acid. The hydroxide ion accepts a H+; it acts as a
Bronsted-Lowry base. Then we have two acids and two
bases.
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)
Base

acid

conjugate

conjugate
acid

base

A conjugate acid is the particle formed when a base


gains a hydrogen ion. A conjugate base is the particle
that remains when an acid has donated a hydrogen ion. A
conjugate acid-base pair is two substances that are
related by the loss or gain of a single hydrogen ion.
Water can either donate or accept hydrogen
substance that can act both is called amphoteric.
4. Common Acid & Base
Table 4. Common Acids and Bases
Name
Acids
Acetic acid
Acetylsalicylic

Formula

Locations

HC2H3O2 Vinegar
(aqueous solution)
HC9H7O4 Aspirin

ion.

acid
Ascorbic acid
Citric acid
Hydrochloric acid
Sulfuric acid
Bases
Ammonia

H2C6H6O6 Vitamin C
H3C6H5O7 Lemon juice, citrus fruits
HCl
Gastric juices
(digestive fluid in stomach)
H2SO4
Batteries
NH3

Household cleaners
(aqueous solution)
Calcium hydroxide
Ca(OH)2 Slaked lime
(used in mortar for construction)
Magnesium hydroxide Mg(OH)2 Milk of magnesia
(antacid and laxative)
Potassium hydroxide KOH
Soft soap
(also called
caustic potash)
Sodium hydroxide
NaOH
Drain and oven cleaners
5. Strength of Acids and Base
Acids are classified as strong or weak depending on the
degree to which they ionize in water.
Strong acids are completely ionized in aqueous solutions
Examples are hydrochloric acid and sulfuric acid. Weak
acids ionize only slightly in aqueous solution.
An acid-base equilibrium always lies in the direction
of the weaker acid.
Acid
Base

Thus, the strongest acids have the weakest conjugate


bases, and the strongest bases have the weakest conjugate
acids.
6. Ionization of H2O
Water shows a very small conduction. That was the result
from self-ionization or autoionization, a reaction in which
two like molecules react to give ions.
In case of water, a proton from one H2O molecule is
transferred to another H2O molecule, leaving behind an OHion and forming a hydronium ion, H3O+ (aq):
H2O (l) + H2O (l) H3O+ (aq) + OH- (aq)
The self-ionization is: H2O (l) H+ (aq) + OH- (aq)
We can see the slight extent to which self-ionization
occurs by the small value of the equilibrium constant, Kc.
An equilibrium constant is the constant value of the
equilibrium-constant value. This expression is obtained by
multiplying the concentrations of the product and dividing
by the concentrations of the reactants, raising each
concentration term to a power equal to the coefficient of
that substance in the chemical equation.

Kc = [H+][OH-]
[H20]
The value of Kc at room temperature is 1.8 x 10 -16. In
water, its concentration remains 56 M at 25 C. Replacing
[H2O] by Kc, then the ionic product [H+] [OH-] equals a
constant:
[H2O]K = [H+][OH-], and the value of the constant is
called the ion-product constant for water (Kw). At 25 C, the
value of Kw is 1.00 x 10-14.
Acidic solution: [H+] > 1.00 x 10-7 M
Neutral solution: [H+] = 1.00 x 10-7 M
Basic solution: [H+] < 1.00 x 10-7 M
7. pH (acid) and pOH (base) concepts
In 1909, Danish scientist Soren Sorensen (1868-1939)
proposed the pH scale. On the pH scale, neutral solutions
have a pH of 7.0. A pH is strongly acidic. The pH of a
solution is the negative logarithm of the hydrogen-ion
concentration.
pH = -log[H+]
In a neutral solution [H+] = 1.0 x 10-7 mol/L. The pH of a
neutral is 7.
pH = -log (1.0 x 10-7 mol/L)
pH = -(log 1 + log 10-7)
pH = -[0.0 + (-7)] = 7.0
Meanwhile, the pOH of a solution equals the negative
logarithm of the hydroxide-ion concentration.
pOH = -log[OH-]
A neutral solution has a pOH of 7.0. A solution with a
pOH less than 7.0 is basic, and higher than 7.0 is acidic.
pH + pOH = 14
pH = 14 pOH
pOH = 14- pH
Neutral solution: pH = 7.0; [H+] = 1 x 10-7 m/L
Acidicl solution: pH < 7.0; [H+] > 1 x 10-7 m/L
Basic solution: pH > 7.0; [H+] < 1 x 10-7 m/L

8. Indicators
An indicator (In) is a weak acid or base that undergoes
dissociation in a known pH range. In this range, the acid
or base is a different color from its conjugate bases or
acid.
Acid

Base

neutral

[H+]
(mol/L)

100

10-1

10-2

10-3

10-4

10-5

10-6

10-7

10-8

10-9

10-10

10-11

10-12

10-13

10-14

pH

10

11

12

13

14

Universal
indicator

red

red

green

darkgreen

blue

blue

blue

blue

blue

cyanidin
(red
cabbage
water)

red

red

red

cerise

purple

blue

blue

blue

lime

lime

blue litmus
indicator

red

red

red

red

red

red

red

blue

blue

blue

blue

blue

blue

blue

blue

5.0 8.0

red litmus
indicator

red

red

red

red

red

red

red

red

blue

blue

blue

blue

blue

blue

blue

5.0 8.0

pink

pink

pink

pink

pink

pink

pink

8.3 10.0

orangepale orange- pale greenorange


red
orange yellow yellow yellow

aqua- emeraldmarine green

pH
range

yellow yellow yellow

phenolphthalein
indicator

colour colour
-less -less

colour
-less

colour colour
-less
-less

colour
-less

thymol
blue
indicator

yellow yellow yellow

yellow yellow

yellow yellow yellow yellow

blue

blue

blue

blue

blue

blue

8.0 9.6

phenol red
yellow yellow yellow
indicator

yellow yellow

yellow yellow yellow

red

red

red

red

red

red

red

6.8 8.4

yellow yellow

yellow yellow

blue

blue

blue

blue

blue

blue

blue

6.2 7.6

bromothymol
blue
indicator
methyl red
indicator
bromocresol
green
indicator
methyl
orange
indicator
bromophenol
blue

yellow yellow yellow

pink

pink

pink

yellow yellow yellow

red

red

red

yellow yellow yellow

cresol red

red

red

red

pH

pink

pink

yellow yellow

red

yellow

yellow

blue

yellow yellow

colour colour
-less
-less

blue

yellow yellow yellow

yellow

yellow yellow yellow yellow yellow

4.4 6.0

bluegreen

bluegreen

bluegreen

blue- blue- blue- blue- bluegreen green green green green

3.8 5.4

yellow yellow yellow yellow

yellow

yellow yellow yellow yellow yellow

3.1 4.4

pink
pale
bluegreen

blue

blue

bluegreen

blue

blue

yellow yellow yellow yellow

blue
yellow

blue

blue

blue

blue

blue

yellow yellow yellow yellow yellow

10

11

12

9. Buffers
Buffer is a solution characterized by the ability to
withstand changes in pH when limited amounts of acid or
base are added to it.

13

14

3.0 4.6
0.2 1.8

pH

Most buffers contain a weak acid and its conjugate base,


or a weak base and its conjugate acid.
For an example, biological fluid such as blood, are
usually buffer solutions because the control of pH is vital
to their proper functioning.
Say, a buffer contains approximately equal molar amounts
of a weak acid HA and its conjugate base, A-. If a strong
acid is added to the buffer, it supplies hydrogen ions that
react with the base A-.
H+ (aq) + A- (aq) HA (aq)
On the other hand, if a strong base is added to the
buffer, it supplies hydroxide ions. These ions react with
the acid HA:
OH- (aq) + HA (aq) H2O (l) + A- (aq)
Thus, a buffer solution resists changes in pH by the
ability to combine with both H+ and OH- ions.
Two important characters of a buffer are the pH and the
buffer capacity, which is the amount of acid or base the
buffer can react with before given a significant pH change.
Buffer capacity depends on the amount of acid and conjugate
base in the solution.
10. Neutralization
Neutralization is a reaction in which an acid and a base
react in an aqueous solution to produce a salt and water.
Examples:
HCl (aq) + NaOH (aq) NaCl (aq) + H2O (l)
H2SO4 (aq) + 2KOH (aq) K2SO4 (aq) + 2H2O (l)
1.1.1.
Titration
The amount of acid or base in a solution can be
determined by carrying out a neutralization reaction.
An appropriate acid-base indicator is used to show
when neutralization has occurred. Phenolpthalein is
often the indicator for acid-base neutralization
reactions. Solutions that contain this indicator turn
from colorless to deep pink as the pH of the solution

is changed from acidic to basic. Neutral solutions are


very faintly pink.
Steps in Titration
1. A measured volume of the unknown concentration is
added to the flask.
2. The indicator is added to the solution.
3. Measured volumes of a base known concentration
are mixed into the acid until the indicator barely
changes color.
Standard
solution
is
the
solution
of
known
concentration. The point at which the indicator
changes color is the end point of the titration.
Thus, titration is the addition of a known amount of
solution of known concentration to determine the
concentration of another solution.
1.1.2.
Equivalents
One equivalent is the amount of an acid (or base)
that will give one mole of hydrogen (or hydroxide
ions).
1.1.3.
Normality
An older unit sometimes used to express the
equivalents of an acid and base is normality.
Normality of a solution is the concentration expressed
as the number of equivalents of solute in 1 L
solution.
A solution containing 1.0 equiv of an acid or base
per liter has a normality of 1.0
Normality (N) = equiv/L
The numerical values of normality and molarity are
equal for acids and bases that give 1 equiv of H+ or
OH- per mole.
The number of equivalents of an acid or base in a
known volume of a solution of known normality can be
calculated.
Number of equivalents of solution = volume (L) of
solution x normality [Equiv = V (L) x N]

Solutions of known morality can be made less


concentrated by diluting them with water. The formula
to calculate the changes in concentration is:
N1V1=N2V2
Titration calculations can be done in terms of
morality instead of molarity since normality allows
number of ionizable hydrogens in an acid whereas
molarity does not. In a titration, the point of
neutralization is called the equivalence point. In
conclusion, it is possible to calculate the number of
equivalents of acid or base in an unknown sample.
Equivalents of acid = NAVA
Equivalents of base = NBVB
1.1.4.
Salt Hydrolysis
The cations or anions of the dissociated salt accept
hydrogen ions from water or donate hydrogen ions to
water. Hydrolyzing salts are usually derived from a
strong acid and a weak base or from a weak acid and a
strong base.
1.1.5.
Solubility Product Constant
Most insoluble salts dissolve to some extent in
water. These salts are said to be slightly or
sparingly soluble in water.
Solubility product constant, Ksp, is equal to the
product of the concentration terms each raised to the
power of the coefficient of the substance in the
dissociation equation.
Actetates
AgC2H3O2 -- 2 x 10-3
Bromides
AgBr -- 5 x 10-13
PbBr2 -- 5 x 10-6
Carbonates
BaCO3 -- 2 x 10-9
CaCO3 -- 5 x 10-9
MgCO3 -- 2 x 10-8

Chlorides
AgCl -- 1.6 x 10-10
Hg2Cl2 -- 1 x 10-18
PbCl2 -- 1.7 x 10-5
Chromates
Ag2CrO4 -- 2 x 10-12
BaCrO4 -- 2 x 10-10
PbCrO4 -- 1 x 10-16
SrCrO4 -- 4 x 10-5
Fluorides
BaF2 -- 2 x 10-6

CaF2 -- 2 x 10-10
PbF2 -- 4 x 10-8
Hydroxides
Al(OH)3 -Cr(OH)3 -Fe(OH)2 -Fe(OH)3 -Mg(OH)2 -Zn(OH)2 --

5
4
1
5
1
5

x
x
x
x
x
x

10-33
10-38
10-15
10-38
10-11
10-17

Iodides
AgI -- 1 x 10-16
PbI2 -- 1 x 10-8

Sulfates
BaSO4 -- 1.4 x 10-9
CaSO4 -- 3 x 10-5
PbSO4 -- 1 x 10-8
Sulfides
Ag2S -- 1 x 10-49
CdS -- 1 x 10-26
CoS -- 1 x 10-20
CuS -- 1 x 10-35
FeS -- 1 x 10-17
HgS -- 1 x 10-52
MnS -- 1 x 10-15
NiS -- 1 x 10-19
PbS -- 1 x 10-27
ZnS -- 1 x 10-20

1.1.6.
Common Ion Effect
In
a
saturated
solution
of
equilibrium is established between
chloride and its ions.

silver
chloride
the solid silver

AgCl (s) Ag+ (aq) + Cl-(aq) Ksp = 1.8 x 10-10


If you would add silver nitrate, the product of the
[Ag+] and [Cl-] would be greater than Ksp. Applying Le
Chateliers principle, the stress of the additional Ag+
can be relieved if the reaction shifts to the left. In
our example, silver ion is the common ion.
Common ion is an ion that is common to both salts.
The lowering of the solution of a substance by the
addition of a common ion is called common ion effect.
11. Salts
Salts are often prepared by neutralization of the
appropriate acid and base.
Properties of Salts
Salts are characterized by ionic bonds, relatively high
melting points, electrical conductivity when melted or when
in solution, and a crystalline structure in solid state.
Table 11.1 Common salts and their applications
NAME
FORMULA
APPLICATIONS
Ammonium sulfate
(NH4)SO4
Fertilizer

Barium sulfate

BaSo4

Calcium chloride

CaCl2

Calcium sulfate
dihydrate (gypsum)
Copper sulfate
pentahydrate (blue
vitriol)
Calcium sulfate
sesquihydrate
Potassium chloride

CaSO42H2O

Gastrointestinal
studies; white
pigment
Deicing roadways
and sidewalks
Plasterboard

CuSO45H2O

Dyeing, fungicide

CaSO41/2H2O

Plaster casts

KCl

Potassium
permanganate
Silver nitrate
Silver bromide

KMnO4

Sodium hydrogen
carbonate (baking
soda)
Sodium carbonate
decahydrate
(washing soda)
Sodium chloride
(table salt)

NaHCO3

Sodium-free salt
substitute
Disinfectant and
fungicide
Cauterizing agent
Photographic
emulsions
Antacid

Sodium thiosulfate
(hypo)

Na2S2O3

AgNO3
AgBr

Na2CO310H2O

Glass manufacture;
water softener

NaCl

Body electrolyte;
chlorine
manufacture
Fixing agent in
photographic
process