lec 3

1
 Solutions
•Solutions can be in many different forms.

Solid – solid: solution of two solids, sterling silver (Cu in Ag) or bronze
(Zn in Cu).
•Gas – gas: standard atomsphere is a solution of multiple gases.
Solid – liquid: salt water

Solvent – the component of the solution present in the greatest

amount.
Solute – the component of the solution present in the smaller amount.

Note:
by adding a solute, the boiling point of a liquid increases and the
freezing point of a liquid decreases (compare to a pure solvent).
2
Saturated solution:
•when a solution contains all the solute it can hold at a given
temperature, we call the solution saturated.

Unsaturated solution:
•any solution containing a lesser amount of solute than a
saturated solution at a given temperature is unsaturated (so
we can dissolve more solute in the solvent).

Supersaturated solution:
•when a solution contains more solute in the solvent than it
can normally hold at a given temperature under equilibrium
conditions.
A supersaturated solution is not stable; when disturbed in any
way, such as by stirring or shaking, the excess solute
3
precipitates.
Solubility:

• the maximum amount of a solute that will dissolve in a

given amount of a particular solvent (at a given
temperature).

•Note: The more similar two compounds are (similar in

term of polarity), the more likely that one will be soluble
in the other. Like dissolves like. Polar compounds
dissolve in polar solvents, and nonpolar compounds
dissolve in nonpolar solvents.

Example,
•Water dissolves NaCl (two polar compounds) and CCl 4
dissolves C6H14 (two nonpolar compounds). 4
Factors affecting solubility:

1) Molecular Interactions
•Strong attraction between solute and solvent result in higher
solubility.
• Due to dipole-dipole interactions polar solutes will dissolve
polar solvents.
• In water the ability to H-bond will increase solubility.

•Miscible: some liquids are completely soluble in other

liquids to form a solution (no matter
•what quantities of each are mixed) (for example: methanol
and water).
•Immiscible: some liquids cannot mix together and they
produce the different phases (for example: oil and water). 5
2) Pressure

•Solubility of gases affected by pressure

• Increasing the pressure of a gas above a liquid increases
the number of interactions with the liquid surface.
• A new equilibrium is established with a higher solute
concentration in the liquid.

Henry’s law: the solubility of a gas in a liquid is directly

proportional to the pressure (the higher the pressure, the
greater the solubility of a gas in a liquid). Pressure has little
effect on the solubility of liquids or solids.

6
3) Temperature

•Solubility of most solid solutes in water increases as the

temperature increases.
•Solubility of gases decreases with increasing temperature.
• Decrease in solubility is mainly due to increased kinetic
energy.
• Decreased solubility at increased temperature is the reason
for thermal pollution of waterways .
• Also why a warm soda goes flat.
•

7
8
4) Concentration
amount of a solute dissolved in a given quantity of solvent.
Many methods of expressing concentration exist. We learn
the three most important here:

Various ways of expressing concentration.

•Mass percentage (ppm, ppb) – mass of solute / mass

solution
• Mole fraction – moles of solute / total moles
•Molarity – moles solute / liters solution
•Molality – moles solute / kg of solvent

9
Percent Concentrations
Expressed as a ratio of the amount of solute to the total
amount of solution:

grams

Weight of solute
Concentration =
X 100
volumeof solution
(%, w/v)

mL

10
Percent Concentrations
Expressed as a ratio of the amount of solute
to the total amount of solution:
mass (grams)

Weight of solute
Concentration = X 100
Weight of solution
(%, w/w)

mass unit (grams)

11
Percent Concentrations
Expressed as a ratio of the amount of solute to the total
amount of solution:

grams

Volume of solute
Concentration =
X 100
Volume of solution
(%, v/v)

mL

12
Molarity:
the number of moles of solute dissolved in 1 liter (L) of solution. The
units of molarity are moles per liter.

moles solute (n)

Molarity (M) =
Volume of solution (L)

Molarity (M) × Volume of solution (L) = number of moles (n)

•A mole is the amount of pure substance containing the same number

of chemical units as there are atoms in exactly 12 grams of carbon-12
(i.e., 6.023 X 1023) Avogadro’s number.

• A practical definition for a mole is that one mole of a substance is the

molecular mass (weight) or formula weight of the substance expressed
in grams.
13
Pert per million (ppm) and part per billion (ppb): for very
dilute solutions.

g solute
ppm = × 106
g solvent

g solute
ppb = × 109
g solvent

One ppm is equivalent to 1 milligram of something per liter

of water (mg/L) or 1 milligram of something per kilogram
soil (mg/kg) 14
Molality

15
Mole fraction – moles of solute / total moles

16
•Dilution:
we frequently prepare solutions by diluting concentrated
solutions (stock solutions)

•rather than by weighing out pure solute.

•When we add only solvent during dilution, the number of
moles of solute remains unchanged:

M1V1 = moles before dilution

M2V2 = moles after dilution

Therefore,
M1V1 = M2V2
%1V1 = %2V2 (using percent concentrations) 17
Water as solvent

• Form aqueous solutions

• Many biological fluids are solutions or have solution

components

• One of best solvents for dissolving ionic substances

• Poor solvent for non-polar covalent substances.

18
Hydrate and hydration:
•when a solid ionic compound is added to water, water
molecules surround the ions at the surface of the crystal.

•Water is a polar molecule. The negative ions (anions) attract

the positive poles of water molecules, and the positive ions
(cations) attract the negative poles of water molecules. Each
ion attracts multiple water molecules and the ion remove
from the crystal.

•We say ions are hydrated and this phenomenon is called

hydration (a more general term, covering all solvents, is
solvated).

19
Water:

Positive ions associate with negative ends of waters, and negative

ions associate with positive ends of waters.

+/- forces
release energy
Na+ Cl-
20
•Electrolyte:
•substances that conduct an electric current when dissolved in
water or when in the molten state are called electrolytes.
These substances can be ionized and produce ions.

•The positively charged ions (cations) migrate to the negative

electrode (cathode) and the negatively charged ions (anions)
migrate to the positive electrode (anode). The movement of
•ions constitutes an electric current.

•Note: compounds that dissociate (ionize) completely are

called strong electrolytes (most of the ionic compounds and
some acids). Compounds that dissociate partially are called
weak electrolytes (such as CH3COOH).
•Compounds that do not dissociate (do not conduct
21
electricity) are called non-ectrolytes (such as distilled water).
Solubility of covalent compounds in water:

•some acids are soluble in water. Covalent compounds will

dissolve in water if they can form hydrogen bonds with water.

•In general, they should have no more than three C atoms for
each O or N atom.

•For example: acetic acid, CH3COOH, is soluble in water, but

benzoic acid, C6H5COOH, is not.

•The exception to this generalization is the rare case where a

covalent compound reacts with water - for instance, HCl.

22
Colloids

•Colloid solute particles range between 0 – 1000 nm.

The colloids are not uniform and transparent (they appear
cloudy and milky).

•Colloidal systems are stable and their components do not

separate on standing (for example: milk, butter, smoke,
and fog).

•Individual colloid particles are large enough to scatter

light called the Tyndall effect

23
Brownian motion:

•Colloidal particles are in constant motion in a solvent

(randomly). For example, the motion of the dust particles
dispersed in air.
•This motion creates favorable conditions for collisions
between particles.

• Why do colloidal particles remain in solution despite all

the collisions?

1. Most colloidal particles carry a large solvation layer.

They do not actually touch eachother; instead, only their
solvent layers collide.
2. All colloids in a particular solution acquire the same kind
24
of charge. Therefore, the like charges repel each other.
•Emulsion:
a mixture of immiscible substances (liquid-liquid). Emulsion is
a type of the colloidal systems (usually as droplets of larger
than colloidal size). The emulsion systems are usually stable.
Milk and mayonnaise are two examples of the emulsion
systems.

•Suspension:
when the diameter of the solute particles is greater than 1000
nm, we have a suspension system. Suspension is not a type of
the colloidal systems. The suspension systems are not stable
and separate into phases (for example: sand in water).

25
Osmosis:

•The movement of solvent molecules

across a semipermeable membrane will
depend on the solute concentration
• the net movement of solvent is always
toward the solution with the higher
solute concentration

Osmotic membrane (semipermeable

membrane): is a selective membrane
that contains very tiny pores, large
enough to allow solvent molecules to
pass through them but not the larger
solvated molecules. 26
Osmotic pressure:

• Imagine that we have a concentrated sugar solution on one

side of a semi-permeable membrane and a dilute sugar
solution on other side.

•Water molecules are smaller than sugar molecules and they

move back and forth across the membrane.

•Water flows from the dilute solution into the concentrated

solution (because molecules will always diffuse from an area
of higher concentration to an area of lower concentration).

•However, sugar molecules cannot pass through the

membrane (because the size of these molecules is bigger).
27
•The amount of external pressure that must be applied to the
more concentrated solution to stop the passage of solvent
molecules across a semipermeable membrane is called
osmotic pressure and this phenomenon is called osmosis.
•The pressure required to prevent osmosis is known as the
osmotic pressure.

Note: The solution of higher concentration always has a

higher osmatic pressure than the one of lower
concentration, which means that the flow of solvent
molecules always occurs from the more dilute solution to
the more concentrated solution.

Osmolarity = M × i
M: molarity; i: number of particles 28
Reverse osmosis

29
Acid Base equilibria in aqueous solutions

The nature of Acid and base

In water Chemistry the use of term acids and bases are used
to distinguish the presence of H+ and OH – ions in solution
respectively.

A common acid is hydrochloric acid (stomach acid ) which

dissociates in water as follow:
HCl  H+ + Cl-
A common base is NaOH (lye) which dissociates in water as
follows:
NaOH  OH- + Na+

30
 Acids and Bases
• Arrhenius definition:
Acid: substance that increases [H3O+] in solution;
Base: substance that increases [OH-] in solution;

• Brnsted-Lowry definition:
Acid: reactant that donates proton in a reaction;
Base: reactant that accepts proton in a reaction;

• Lewis definition: - in the formation of covalent bonds,

Acid: one that accept electron-pairs
Base: one that donate electron-pairs
31
 Brønsted-Lowry: Conjugate Acids &
Bases
• Consider the following equilibrium:
HA + B ⇌ BH+ + A-;
Acid1 Base2 Conjugate Conjugate
acid2 base1
• A- is the conjugate base to acid HA;
HA & A- are conjugate acid-base pair;
• BH+ is the conjugate acid to base B;
BH+ & B are also conjugate acid-base pair.

32
Brønsted-Lowry’s Acid-Base Reaction

33
 The Conjugate Pairs in Some Acid-Base Reactions
Conjugate Pair

Acid + Base Base + Acid

Conjugate Pair

Reaction 1 HF + H2O F– + H3O+

Reaction 2 HCOOH + CN– HCOO– + HCN

Reaction 3 NH4+ + CO32– NH3 + HCO3–

Reaction 4 H2PO4– + OH– HPO42– + H2O

Reaction 5 H2SO4 + N2H5+ HSO4– + N2H62+

Reaction 6 HPO42– + SO32– PO43– + HSO3– 34

 Relative Strength of Acids and Their
Conjugate Bases
Acids Conjugate Bases
Very Strong Very Weak
Strong Weak
Weak Strong
Very Weak Very Strong
______________________________
• Strong acids lose protons very readily  weak
conjugate bases;
• Weak acids do not lose protons very readily  strong
conjugate bases.
35
 Autoionization of Water
In pure water (no solute) water molecules behave as both an
acid and base!!
e.g.
H2O (l) + H2O (l)  H3O+ (aq) + OH- (aq)

This is called the self-ionization (autoionizaion) of water.

Although the equilibrium lies far to the left it is very
important to take into consideration, especially for living
systems.

36
 Acid-Base Properties of Water
• Auto-ionization of water:
2H2O  H3O+(aq) + OH-(aq)
• The equilibrium constant for this reaction is given by:

[H3O  ][OH ] [H3O  ][OH ]

K 
[H2O ][H2O ] [H2O ]2
K[H2O ]2 K w [H3O  ][OH ]

Kw is ion product of water and its value is :

Kw = [H3O+][OH-] = 1.0 x 10-14 at 25oC

• Water ionizes to produce both H3O+ and OH-, thus it has both
acid and base properties. Kw is called water ionization constant.
• Pure water at 25oC: [H3O+] = [OH-] = 1.0 x 10-7 M 37
 Calculation of pH and pOH

• pH AND pOH (note: [H+] = [H3O+])

• The terms pH and pOH were devised as a means of

expressing H3O+ and OH- activity without using exponents.
• pH is the negative logarithm of the H+ activity. The original
meaning of "p" was "potential", in this case potential of
H3O+.
• Similarly, pOH is the negative logarithm of the OH- activity.
• In dilute solution the activities of H3O+ and OH- are
considered to be the same as their concentrations.
Therefore in dilute solutions:
• pH = -log[H3O+] and pOH = -log[OH-] and
38
The ion product expression for the ionization of water
may be rearranged as follows to yield a useful
equation.
Kw = [H3O+] [OH-]

•Substitute 1 x 10-14 for Kw at 25°C and take logarithms.

log[H3O+] + log[OH-] = -14

multiply by -1
-log[H3O+] + (- log[OH-]) = 14

therefore
pH + pOH = 14 39
 Acidity and pH Range

• Acidic solutions:
[H3O+] > 1.0 x 10-7 M; pH < 7

• Basic solutions:
[OH-] > 1.0 x 10-7 M or [H3O+] < 1.0 x 10-7 M
pH > 7

• Neutral solutions:
[H3O+] = [OH-] = 1.0 x 10-7 M; pH = 7.00
40
Relationship between acidity of solution and pH

41
 [H3O+] and pH of Strong Acids
• Strong acids like HCl and HClO4 ionize completely in
aqueous solution:
HCl(aq) + H2O  H3O+(aq) + Cl-(aq);
HClO4(aq) + H2O  H3O+(aq) + ClO4-(aq);

• In solutions of strong monoprotic acids HA, such as

HCl and HClO4, [H3O+] = [HA]0

• For example, in 0.10 M HCl,

[H3O+] = 0.10 M, and pH = -log(0.10) = 1.00

42
 -
[OH ] and pH of Strong Bases
• Like strong acids, strong bases also ionize completely in aqueous
solution.
NaOH(aq)  Na+(aq) + OH-(aq);
Ba(OH)2(aq)  Ba2+(aq) + 2 OH-(aq);
• In a base solution such as 0.050 M NaOH,
[OH-] = [NaOH]0 = 0.050 M;
pOH = -log(0.050 M) = 1.30; pH = 14.00 - 1.30 = 12.70

• In a base solution such as 0.050 M Ba(OH)2,

[OH-] = 2 x [Ba(OH)2]0 = 0.10 M;
pOH = -log(0.10) = 1.00; pH = 14.00 - 1.00 = 13.00
43
 Acid Strength and Ionization Constants
For the ionization or dissociation equilibrium of an acid in aqueous solution, such
as:
HA(aq) + H2O  H3O+(aq) + A-(aq);
The ionization or dissociation constant is expressed as follows:
 -
[H 3O ][A ]
Ka 
[HA]
• The values of Ka indicate the relative strength of the acids.

• Strong acids have very large Ka (very small amount of undissociated acid so
immeaurable)

• while weak acids have small Ka’s (Ka << 1)(which is mearuable).

Ka, the acid ionization constant, is the equilibrium constant for chemical reactions
44
 [H3O+] and pH of Weak Acids

• In weak acid solutions, [H3O+] < [HA]0

• [H3O+] and pH can be calculated from the initial

concentration of the acid and its Ka value.

• For example, in 0.100 M acetic acid, CH3COOH,

Ka = 1.8 x 10-5, [H3O+] and

pH can be calculated using the “ICE” table.
45
 ICE Table for Acetic Acid

• Ionization: CH3CO2H + H2O  H3O+ + CH3CO2-

• 
• Initial [M] 0.100 0.00 0.00
• Change [M] -x +x +x
• Equilm. [M] (0.100 – x) x x
• 

  2
[H 3O ][CH 3CO 2 ] x -5
Ka   1.8 x 10
[CH 3COOH] (0.100 - x )
46
 Calculating [H3O+] from initial concentration
and Ka by approximation method.

• Solving for x in the expression for Ka:


[H 3O  ][CH 3CO 2 ] x2
Ka   1.8 x 10-5
[CH 3CO 2 H] (0.100 - x )
K a  [HA]0 (1.8 x 10-5  0.100)  x  0.100,
x2 x2
and (0.10 - x ) ~ 0.10. This makes ~ 1.8 x 10-5 ;
(0.100 - x ) 0.100
x 2 (0.100)(1.8 x 10-5 ) 1.8 x 10-6 ; and x  1.8 x 10-6 1.34 x 10-3 ;
[H 3O  ] x 1.34 x 10-3 M; pH - log(1.34 x 10-3 ) 2.873

47
 Calculation Percent Ionization

[HA]ionized x
% Ionization  100%  x 100
[HA]initial (0.100 - x )

• We calculated that, in 0.10 M CH3COOH, the

concentration of acid that ionizes is 1.34 x 10 -3 M.
• The percent ionization of 0.10 M acetic acid:

1.34 x 10 -3 M
% ionization ~ x 100% 1.34%
0.100
48
 Increase in Percent Ionization with
Dilution

• Percent ionization of weak acid increases as the

dilution increases.

• For example, if [CH3COOH]initial = 0.0100 M

• [CH3COOH]ionized ~ 4.24 x 10-4 M (calculated using

approximation method);

4.24 x 10-4
Percent ionization  x 100 4.24%
0.0100
49
 Percent Ionization Increases with
Dilution
• At [CH3COOH]initial = 0.00100 M,

• [CH3COOH]ionized = 1.34 x 10-4 M (by approximation)

1.34 x 10-4
Percent ionization  x 100 13.4%
0.00100

• The more we dilute the acid solution, the higher the fraction
of the acid that will ionize, which increases the degree of
ionization.

• Its related to the Le Chatelier’s principle 50

Classifying the Relative Strengths of Acids and Bases–I

Strong acids. There are two types of strong acids:

1. The hydrohalic acids HCl, HBr, and HI

2. Oxoacids in which the number of O atoms exceeds the number of
ionizable H atoms by two or more, such as HNO3, H2SO4, HClO4

Weak acids. There are many more weak acids than strong ones. Four
types, with examples, are:

1. The hydrohalic acid HF

2. Those acids in which H is bounded to O or to halogen, such as
HCN and H2S
3. Oxoacids in which the number of O atoms equals or exceeds by
one the number of ionizable H atoms, such as HClO, HNO2, and H3PO4
4. Organic acids (general formula RCOOH), such as CH3COOH and
51
C H COOH
Dissociations of Strong and Weak Acids

52
 Base Strength and Ionization Constants
• For the ionization or dissociation equilibrium of a base in aqueous
solution, such as:

The ionization or dissociation constant is expressed as follows:

• The values of Kb indicate the relative strength of the base.

• Strong bases have very large Kb (very small amount of
undissociated base so immeaurable),
• while weak bases have small Kb’s (Kb << 1)(which is mearuable).

Kb, the base ionization constant, is the equilibrium constant for

chemical reactions involving weak acids in aqueous solution. 53
 [OH-] and pH of a Weak Base
• In a weak base, [OH-] < [Base]0;

• [OH-] and pH can be calculated from the initial

concentration of the base and its Kb value.

• For example, in 0.100 M ammonia, NH3,

Kb = 1.8 x 10-5, [OH-] and
pH can be calculated using the following “ICE” table.

54
ICE Table for the Ionization of Ammonia

• Ionization: NH3 + H2O  NH4+ + OH-

• 
• Initial [M] 0.100 0.00 0.00
• Change [M] -x +x +x
• Equilm. [M] (0.100 – x) x x
• 

[NH 4 ][OH - ] x2
Kb   1.8 x 10  5
[NH 3 ] (0.100  x )

55
 Calculate [OH-] from initial concentration
and Kb by approximation method.

• Solving for x in the expression for Kb:

[NH 4 ][OH - ] x2
Kb   1.8 x 10  5
[NH 3 ] (0.100  x )
K b  [B]0 (1.8 x 10 -5  0.100)  x  0.100, and
x2 x2
(0.100 - x ) ~ 0.100, which makes ~ 1.8 x 10 -5 ;
(0.100 - x ) 0.100
x 2 (0.100)(1.8 x 10 -5 ) 1.8 x 10 -6 , which yields x 1.34 x 10 -3 ;
[OH - ] 1.34 x 10 -3 M  pOH 2.873, and pH 11.127
56
Classifying the Relative Strengths of Acids and Bases–II

Strong bases. Soluble compounds containing O2- or OH- ions are strong
bases. The cations are usually those of the most active metals:

1) M2O or MOH, where M= Group 1A(1) metals (Li, Na, K, Rb, Cs)
2) MO or M(OH)2, where M = Group 2A(2) metals (Ca, Sr, Ba)
[MgO and Mg(OH)2 are only slightly soluble, but the soluble
portion dissociates completely.]

Weak bases. Many compounds with an electron-rich nitrogen are weak

bases (none are Arrhenius bases). The common structural feature
is an N atom that has a lone electron pair in its Lewis structure.

1) Ammonia (:NH3)
:

: :
:

2) Amines (general formula RNH2, R2NH, R3N), such as

:

CH3CH2NH2, (CH3)2NH, (C3H7)3N, and C5H5N 57

 The Relation Between Ka and Kb of a Conjugate
Acid-Base Pair

Acid HA + H2O H3O+ + A-

Base A- + H 2 O HA + OH-

water 2 H2 O H3O+ + OH-

Kw = Ka x Kb

[H3O+] [A-] [HA] [OH-]

[H3O+] [OH-] = x
[HA] [A-]
For HNO2 Ka = 4.5 x 10-4 Kb = 2.2 x 10-11

Ka x Kb = (4.5 x 10-4) x (2.2 x 10-11) = 9.9 x 10-15

58
or ~ 10 x 10 -15
= 1 x 10 -14
= Kw
 Polyprotic Acids
• Acids with more than one ionizable hydrogen ion, such as
H2SO3, H2SO4, H3PO4, H3C6H5O7, etc.

• Their hydrogen ionizes in stages, for example,

H3PO4(aq) + H2O ⇄ H3O+(aq) + H2PO4-(aq); Ka1 = 7.5 x 10-3
H2PO4-(aq) + H2O ⇄ H3O+(aq) + HPO42-(aq); Ka2 = 6.2 x 10-8
HPO42-(aq) + H2O ⇄ H3O+(aq) + PO43-(aq); Ka3 = 4.8 x 10-13

Acid strength decreases in the order:

H3PO4 >> H2PO4- >> HPO42-;

pH of solution is determined mainly by ionization of H3PO4

59
SALTS

•A salt is an ionic compound containing an anion other

than OH- or O2-.
•Almost all salts dissolve completely in water at
concentrations commonly used in biological research.

•A salt consists of ions both when in the solid form and

when dissolved in water.

•For many salts dissolved in water, one or more of the

ions react with water to form significant amounts of
either H3O+ or OH-,
•that is, the ions act as weak acids or bases or both. The
reaction is termed a hydrolysis. 60
For example,

when NH4Cl is dissolved in water the ions, NH4+ and

Cl- react with water. A small fraction of the NH4+ reacts as
follows:

NH4+ + H2O <===> NH3 + H3O+

Although only a small fraction reacts, it is sufficient to

make the solution acidic.

Cl- does not react to any significant extent.

Cl- + H2O ==> no significant reaction

61
 Acid-Base Properties of Salt Solutions
• The acid-base property of a salt solution depends on
whether the compound is a product of:

1. Strong acid-strong base reaction: produces neutral

salt
2. Strong acid-weak base reaction: produces acidic
salt
3. Strong base-weak acid reaction: produces basic
salt
4. Weak acid-weak base reaction: produces salt that
is either acidic or basic, depending on the relative
strength of the acid and the base.
62
 Types of Salts and Their Solutions
• Salts of Strong Acid-Strong Base Reactions:
NaCl, NaNO3, KBr, etc.; solutions are neutral
• Salts of Weak Acid-Strong Base Reactions:
NaF, NaNO2, NaC2H3O2, etc.; solutions are basic
• Salts of Strong Acid-Weak Base Reactions:
NH4Cl, NH4NO3, (CH3)2NH2Cl, C5H5NHCl;
Solutions of these salts are acidic
• Salts of Weak Acid-Weak Base Reactions:
NH4C2H3O2, NH4CN, NH4NO2, etc..
These compounds can be acidic, basic, or neutral,
which depends on the relative strength of the acid and
the base. 63
 Salts of Strong Acid-Strong Base Reactions

• Dissociation and reaction of a neutral salt:

NaCl(aq)  Na+(aq) + Cl-(aq);

Na+(aq) + H2O  NR
Cl- (aq) + H2O  NR

(The concentrations of H3O+ and OH- in NaCl

solution are the same as in pure water  solution is
neutral.)

64
 Salts of Weak Acid-Strong Base Reactions:

• Dissociation and reaction of a basic salt:

NaNO2(aq)  Na+(aq) + NO2-(aq);

Na+(aq) + H2O  NR
NO2-(aq) + H2O  HNO2(aq) + OH-(aq)

(The reaction of NO2- with water causes [OH-] >

[H3O+] and the solution becomes basic.)

65
 Salts of Strong Acid-Weak Base Reactions

• Dissociation and reaction of an acidic salt:

NH4NO3(aq)  NH4+(aq) + NO3-(aq);

NH4+(aq) + H2O  NH3(aq) + H3O+(aq);
NO3-(aq) + H2O  NR;

• (The reaction of NH4+ with water causes [H3O+] >

[OH-], and the solution becomes acidic.)

66
 Salts of Weak Acid-Weak Base Reactions
• Salts produced by reactions of weak acids and weak
bases can be neutral, acidic, or basic, depending on
the relative magnitude of the Ka of the weak acid
and the Kb of the weak base.

• If Ka ~ Kb, salts are neutral; example: NH4C2H3O2

• If Ka > Kb, salts are acidic; example: NH4NO2
• If Ka < Kb, salts are basic; example: NaC2H3O2

67
 Predicting Acid-Base Property of Salts

• Consider a solution containing NH4C2H3O2

NH4C2H3O2(aq)  NH4+(aq) + C2H3O2-(aq);

NH4+(aq) + H2O  H3O+(aq) + NH3(aq); Ka = 5.6 x 10-10

C2H3O2-(aq) + H2O  HC2H3O2(aq) + OH-(aq); Kb = 5.6 x 10-10

Ka = Kb = 5.6 x 10-10,  NH4C2H3O2 is neutral

68
 Predicting Acid-Base Property of Salts

• Consider a solution containing (NH4)2SO4

(NH4)2SO4(aq)  2NH4+(aq) + SO42-(aq);

NH4+(aq) + H2O  H3O+(aq) + NH3(aq); Ka = 5.6 x 10-10

SO42-(aq) + H2O  HSO4-(aq) + OH-(aq); Kb = 8.3 x 10-13

Ka > Kb  (NH4)2SO4 is acidic;

69
Predicting Acid-Base Characteristics of Salts

• Now consider a solution containing NH4CN.

NH4CN(aq)  NH4+(aq) + CN-(aq);

NH4+(aq) + H2O  H3O+(aq) + NH3(aq); Ka = 5.6 x 10-10

CN-(aq) + H2O  HCN(aq) + OH-(aq); Kb = 1.6 x 10-5

Kb > Ka  NH4CN is basic

70
HENDERSON-HASSELBALCH EQUATION

•Many biological compounds are weak acids or weak bases

or both. Researchers often want to know what proportion of
such biological compounds are in the conjugate acid and
conjugate base forms at a particular pH.. The Henderson-
Hasselbalch equation relates these values The derivation of
this equation is described.

71
Dissociation of a weak acid is mathematically described by the
Henderson-Hasselbalch equation

Ka = [H+ ][A- ] / [HA] or

Ka = [H+ ] x [A- ] / [HA] take log

logKa = log[H+ ] + log {[A- ] / [HA]} arrange to calculate [H+ ]

-log[H+ ] = -logKa + log {[A- ] / [HA]}

pH = pKa + log {[A- ] / [HA]}

This is the Henderson-Hasselbalch equation

Where, [A- ] = conjugate base and [HA] = weak acid,

Note: pH = pKa when [A- ] = [HA] 72

 Common ion effect
•The common ion effect is responsible for the reduction in
the solubility of an ionic precipitate when a soluble compound
containing one of the ions of the precipitate is added to the
solution in equilibrium with the precipitate.

• It states that if the concentration of any one of the ions is

increased, then, according to Le Chatelier's principle, some of
the ions in excess should be removed from solution, by
combining with the oppositely charged ions.

• Some of the salt will be precipitated until the ion product is

equal to the solubility product. In short, the common ion
effect is the suppression of the degree of dissociation of a
weak electrolyte containing a common ion. 73
74
 Solubility product
The solubility product constant, Ksp, is the equilibrium
constant for a solid substance of relatively low solubility
dissolving in an aqueous solution. It represents the level
at which a solute dissolves in solution. The more soluble a
substance is, the higher the Ksp value it has.
Consider the general dissolution reaction below (in
aqueous solutions):
aA(s) ⇌ cC(aq)+dD(aq)

To solve for the Ksp it is necessary to take the molarities

or concentrations of the products (cC and dD) and
multiply them. If there are coefficients in front of any of
the products, it is necessary to raise the product to that
coefficient power(and also multiply the concentration by
that coefficient). This is shown below:
75
Note that the reactant, aA, is not included in the
Ksp equation.

Solids are not included when calculating

equilibrium constant expressions, because their
concentrations do not change the expression; any
change in their concentrations are insignificant,
and therefore omitted.

Hence, Ksp represents the maximum extent that

a solid that can dissolved in solution.

76
 Buffers
•A buffer is a solution that resists changes in pH when acid
or base are added to it.

•A buffer consists of a solution of a weak acid and the

corresponding conjugate base. One can also state it consists
of a solution of a weak base and its conjugate acid.

77
 How buffers work
• Equilibrium between acid and base.

• Example: Acetate buffer

CH3COOH  CH3COO- + H+

• If more H+ is added to this solution, it simply shifts

the equilibrium to the left, absorbing H+, so the [H+]
remains unchanged.

• If H+ is removed (e.g. by adding OH-) then the

equilibrium shifts to the right, releasing H+ to keep
the pH constant
78
Limits to the working range of a buffer
• Consider the previous example:
CH3COOH  CH3COO- + H+

• If too much H+ is added, the equilibrium is shifted

all the way to the left, and there is no longer any
more CH3COO- to “absorb” H+.

• At that point the solution no longer resists

change in pH; it is useless as a buffer.

• This is als called as buffer capacity.

79
Buffer Capacity

•The buffer capactity refers to the maximum amount of either

strong acid or strong base that can be added before a
significant change in the pH will occur. This is simply a matter
of stoichiometry.

•The maximum amount of strong acid that can be added is

equal to the amount of conjugate base present in the buffer.

•The maximum amount of base that can be added is equal to

the amount of weak acid present in the buffer.

•Most efficient buffer is when

[A-]
[HA] = 1
80
• Example: Determine the pH in which 1.00
mole of H2CO3 (Ka = 4.2 x 10-7) and 1.00 mole
NaHCO3 dissolved in enough water to form
1.00 Liters of solution.
[A-]
pH = pKa + log
[HA]

pH = -log (4.2 x 10-7) + log (1.00M)/(1.00M)

pH = pKa = 6.4
** pKa of a weak acid can help determine pH of buffer you
will make if it is mixed in a 1:1 mole ratio! 81
 Factors in choosing a buffer
• Choose a compound whose pKa is close to the pH for the
solution
• Determine what the buffer concentration should be.
• Be sure it covers the pH range you need
– Generally: pKa of acid ± 1 pH unit
– Consult tables for ranges or pKa values

• Be sure it is not toxic to the cells or organisms you are

working with.
• Be sure it would not confound the experiment (e.g. avoid
phosphate buffers in experiments on plant mineral
nutrition). 82
 Make a buffer problem
• How many moles of NaHCO3 should be added to 1 liter
of 0.100M H2CO3 (Ka = 4.2 x 10-7 ) to prepare a buffer
with a pH of 7.00?
[HCO3-]
pH = pKa + log
[H2CO3]
7.00 = -log(4.2 x 10-7) + log [HCO3-]
(0.100)
0.60 = log[HCO3-]
0.001
[HCO3-] = 0.40 moles should
100.6 = [HCO3-] be added!
0.100 83
 Chemistry of buffers
Titration
Titration is used to determine the concentration of an acid
or base by adding the OTHER and finding an equivalency
point…

84
Suppose you have a KOH
solution, and you want to
know its concentration
(molarity).

Slowly add an acid (HCl) with a

known concentration (0.1 M)
and find the equivalency
point…in this case it will be at
pH = 7… and we use an
indicator that changes color at
that pH determine when that
point has been reached.

So, suppose it takes 10ml of

0.1 M HCl to buffer 50 ml of
the KOH.
85
So, suppose it takes 10ml of 0.1 M HCl to buffer 50 ml of the KOH.

The original conc. of the base = Vol Acid x Conc. of acid

Volume of Base
10 ml x 0.1 M = 0.02 M
50 ml

86