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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.BrØnsted-Lowry Acids and Bases


In 1923, Danish chemist Johannes BrØnsted (1879-1947),
and English chemist Thomas Lowry (1874-1936) independently
proposed a new theory. BrØnsted-Lowry acid is defined as a
hydrogen-ion donor, and a BrØnsted-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.

Table 1. Acid-Base Definitions


Type Acid Base
Arrhenius H producer
+
OH producer
-

BrØnsted-Lowry H+ donor H+ acceptor


Lewis Electron-pair acceptor Electron-pair 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 O
I II
H-C-C-O-H ethanoic acid (C CH3COOH)
I
H

The structural formula shows that the three hydrogens are in weakly
polar bonds.

Table 2. Some Common Acids


Name Formula
Hydrochloric acid HCl
Nitric acid HNO3
Sulfuric acid H2SO4
Phosphoric acid H3PO4
Ethanoic acid CH3COOH
Carbonic acid 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 hydroxide KOH High
Sodium hydroxide NaOH High
Calcium hydroxide Ca(OH)2 Very low
Magnesium hydroxide Mg(OH)2 Very low

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. BrØnsted-Lowry
A Bronsted-Lowry acid is defined as a hydrogen-ion donor, while a
Bronsted-Lowry base is a hydrogen-ion acceptor.

Let’s 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
Bronsted-Lowry 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 ion. A substance


that can act both is called amphoteric.

4. Common Acid & Base

Table 4. Common Acids and Bases


Name Formula Locations
Acids
Acetic acid HC2H3O2 Vinegar
(aqueous solution)
Acetylsalicylic acid HC9H7O4 Aspirin
Ascorbic acid H2C6H6O Vitamin C
6

Citric acid H3C6H5O Lemon juice, citrus fruits


7

Hydrochloric acid HCl Gastric juices


(digestive fluid in stomach)
Sulfuric acid H2SO4 Batteries
Bases
Ammonia 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 OH- ion 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 25º 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 25º 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 neutral Base

[H+]
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
(mol/L)

pH
pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
range

Universal orange- pale orange- pale green- dark-


red red orange green blue blue blue blue blue
indicator red orange yellow yellow yellow green
cyanidin
(red aqua- emerald-
red red red cerise purple blue blue blue lime lime yellow yellow yellow
cabbage marine green
water)
blue litmus
red red red red red red red blue blue blue blue blue blue blue blue 5.0 - 8.0
indicator
red litmus
red red red red red red red red blue blue blue blue blue blue blue 5.0 - 8.0
indicator
phenol-
colour colour colour colour colour colour colour colour
phthalein pink pink pink pink pink pink pink 8.3 - 10.0
-less -less -less -less -less -less -less -less
indicator
thymol blue
yellow yellow yellow yellow yellow yellow yellow yellow yellow blue blue blue blue blue blue 8.0 - 9.6
indicator
phenol red
yellow yellow yellow yellow yellow yellow yellow yellow red red red red red red red 6.8 - 8.4
indicator
bromo-
thymol blue yellow yellow yellow yellow yellow yellow yellow blue blue blue blue blue blue blue blue 6.2 - 7.6
indicator
methyl red
pink pink pink pink pink pink yellow yellow yellow yellow yellow yellow yellow yellow yellow 4.4 - 6.0
indicator
bromo-
pale
cresol blue- blue- blue- blue- blue- blue- blue- blue- blue-
yellow yellow yellow yellow yellow blue- 3.8 - 5.4
green green green green green green green green green green
green
indicator
methyl
orange red red red red yellow yellow yellow yellow yellow yellow yellow yellow yellow yellow yellow 3.1 - 4.4
indicator
bromo-
yellow yellow yellow yellow blue blue blue blue blue blue blue blue blue blue blue 3.0 - 4.6
phenol blue
cresol red red red red yellow yellow yellow yellow yellow yellow yellow yellow yellow yellow yellow yellow 0.2 - 1.8

pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 pH

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.

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 Cr(OH)3 -- 4 x 10-38
AgBr -- 5 x 10-13 Fe(OH)2 -- 1 x 10-15
PbBr2 -- 5 x 10-6 Fe(OH)3 -- 5 x 10-38
Mg(OH)2 -- 1 x 10-11
Carbonates Zn(OH)2 -- 5 x 10-17
BaCO3 -- 2 x 10-9
CaCO3 -- 5 x 10-9 Iodides
MgCO3 -- 2 x 10-8 AgI -- 1 x 10-16
PbI2 -- 1 x 10-8
Chlorides
AgCl -- 1.6 x 10-10 Sulfates
Hg2Cl2 -- 1 x 10-18 BaSO4 -- 1.4 x 10-9
PbCl2 -- 1.7 x 10-5 CaSO4 -- 3 x 10-5
PbSO4 -- 1 x 10-8
Chromates
Ag2CrO4 -- 2 x 10-12 Sulfides
BaCrO4 -- 2 x 10-10 Ag2S -- 1 x 10-49
PbCrO4 -- 1 x 10-16 CdS -- 1 x 10-26
SrCrO4 -- 4 x 10-5 CoS -- 1 x 10-20
CuS -- 1 x 10-35
Fluorides FeS -- 1 x 10-17
BaF2 -- 2 x 10-6 HgS -- 1 x 10-52
CaF2 -- 2 x 10-10 MnS -- 1 x 10-15
PbF2 -- 4 x 10-8 NiS -- 1 x 10-19
PbS -- 1 x 10-27
ZnS -- 1 x 10-20
Hydroxides
Al(OH)3 -- 5 x 10-33

1.1.6.Common Ion Effect


In a saturated solution of silver chloride equilibrium is
established between the solid silver chloride and its ions.

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 Chatelier’s 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 Gastrointestinal
studies; white
pigment
Calcium chloride CaCl2 Deicing roadways and
sidewalks
Calcium sulfate CaSO4∙2H2O Plasterboard
dihydrate (gypsum)
Copper sulfate CuSO4∙5H2O Dyeing, fungicide
pentahydrate (blue
vitriol)
Calcium sulfate CaSO4∙1/2H2O Plaster casts
sesquihydrate
Potassium chloride KCl Sodium-free salt
substitute
Potassium KMnO4 Disinfectant and
permanganate fungicide
Silver nitrate AgNO3 Cauterizing agent
Silver bromide AgBr Photographic
emulsions
Sodium hydrogen NaHCO3 Antacid
carbonate (baking
soda)
Sodium carbonate Na2CO3∙10H2O Glass manufacture;
decahydrate (washing water softener
soda)
Sodium chloride (table NaCl Body electrolyte;
salt) chlorine manufacture
Sodium thiosulfate Na2S2O3 Fixing agent in
(hypo) photographic process