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Physical Chemistry 2

F R E E E N E R G Y A N D E Q U I L I B R I U M

C H E M I C A L E Q U I L I B R I A
S O L U T I O N S O F N O N E L E C T R O L Y T E S
S O L U T I O N S O F E L E C T R O L Y T E S
E L E C T R O C H E M I C A L C E L L S
CHEMICAL EQUILIBRIA

Equilibrium is the state in which the rate at which


the reactants disappear to form products is exactly
equal to the rate at which the products interact to
reform the reacting substances.

All chemical equilibria and physical equilibria


between states are considered dynamic, in contrast
to a static equilibrium where there is no motion
whatsoever.
CHEMICAL EQUILIBRIA

2 groups:
Homogeneous equilibrium is one established in a
system in which only one phase occurs.
Heterogeneous equilibrium is one established in a
system in which more than a single phase appears.
Law of Mass Action

The rate of any reaction is, at each instant, proportional


to the concentration of the reactants with each
concentration raised to a power equal to the number of
moles of each species participating in the process.

Consider the hypothetical reaction:


aA(g) + bB(g) cC(g) + dD(g)

rate of forward reaction:
rate of reverse reaction:
at equilibrium, =

=
CHEMICAL EQUILIBRIA

For gases and aqueous solutions in the chemical reaction,


Kc is used and concentrations are expressed in molarity.
The equilibrium expression is written as



= =

If Kc<<<1 equilibrium lies to the right (more products than reactants)


Kc>>>1 equilibrium lies to the left (more reactants than products)
CHEMICAL EQUILIBRIA

=
Since for gases , the Kc expression will be

+
1
=

=



Thus, we define

=

And
= , ,
Therefore,
CHEMICAL EQUILIBRIA

Kp and Kc Relationship

=
Gibbs-Helmholtz Equation


=
2

Relation of Kp and G
= ()
Temperature Dependence of Kp

=
2
Le Chatelier-Braun Principle

A system in equilibrium when subjected to a


stress will act in such a way to relieve the stress.

Consider the equilibrium reaction:


2 + 32 2 3 H = 45 kJ/mol

Effects of Changing the Concentration


Increasing the concentration of the reactants
shifts the reaction forward
Increasing the concentration of the products
shifts the reaction backward
Le Chatelier-Braun Principle

2 + 32 2 3 H = 45 kJ/mol

Effects of Changing the Pressure/Volume


Increasing the pressure (or similarly decreasing the
volume) of a system in equilibrium
shifts the reaction towards the formation of less
number of gaseous molecules.
On the other hand, decreasing the pressure (or similarly
increasing the volume) of a system in equilibrium
shifts the reaction towards the formation of greater
number of gaseous molecules.
Le Chatelier-Braun Principle

2 + 32 2 3 H = 45 kJ/mol

Effects of Changing the Temperature


Increasing the temperature
favors an endothermic reaction

Decreasing the temperature


favors an exothermic reaction

For the reaction above, increasing the temperature


will favor the backward reaction being exothermic.
Le Chatelier-Braun Principle

2 + 32 2 3 H = 45 kJ/mol

Effect of Adding the Catalyst


Adding a catalyst does not affect the
equilibrium.

Effect of Adding an Inert Gas


At constant pressure, addition of inert gases
would not alter equilibrium.
Dissociation of Gases

Reactants Products
At start: 1 0
At anytime 1- v


=
( )

Where = degree of dissociation


M1, M2 = molecular weights
V= volume
NT = total number of moles (rcts + prods)
Exercise Problems

1. 1.588g of Nitrogen tetroxide gives a total pressure


of 760mmHg when partially dissociated in a
500mL vessel at 25C. Find the degree of
dissociation and kp.
2. The equilibrium constant for the dissociation
2H2S(g) =2H2(g) + S2(g) is Kp=0.0118 at 1065C,
while the heat of dissociation is H=42400cal.
Find the equilibrium constant of the reaction at
1200C. (Maron & Lando, 28/p386)
Physical Chemistry 2

F R E E E N E R G Y A N D E Q U I L I B R I U M
C H E M I C A L E Q U I L I B R I A

S O L U T I O N S O F
N O N E L E C T R OL Y T E S
S O L U T I O N S O F E L E C T R O L Y T E S
E L E C T R O C H E M I C A L C E L L S
SOLUTIONS OF NONELECTROLYTES

Nonelectrolytes
persists in uncharged form and exhibits no tendency
to dissociate into electrically charged ions.
They are solutions that do not conduct
electricity.
These are the solutions which yield for the dissolved
substances normal molecular weights, i.e. the
molecular weights expected from their chemical
formulas.
SOLUTIONS OF NONELECTROLYTES

Important Terms
Solute
Solvent
Solubility
Unsaturated solution
Saturated solution
Supersaturated solution

Factors Affecting Solubility


Nature of the solute and solvent
Temperature
Pressure
Thermodynamic Properties of Solutions

The total free energy of a solution


= + +
Where
1 , 2 =partial molal free energies of the solution constituents
1 , 2 =number of moles of various constituents

Total entropy and enthalpy is then given by


= + +
= + +

Since G=H-TS, it follows


= +
= +
Thermodynamic Properties of Solutions

Partial molal free energy of any constituent of a


solution
= +
where G i : partial molal free energy constituent i in some
suitably chosen standard
ai : its activity in the solution at any given concn

if mol fractions are employed to express concentration


then ai can be related with Ni by the equation
=
where yi : activity coefficient
The Solution Process and Ideal Solutions

The Solution Process



=

= +
=
Where P = pressure of solution
P = P of pure substances
PT = total pressure
Y1 =mole fraction of the vapor

Ideal Solutions
= +
=

=

Colligative Properties
of Nonelectrolytic Solutions
Colligative Property Nonelectrolytes
=
1. Vapor-pressure
lowering Where P=vapor pressure of the pure solvent, xsolute=mole fraction of the
solute in the solution and P=extent of vapor pressure lowering

=
2. Boiling point
elevation Where = , ,
Kb=ebullioscopic constant and m=molality

=
3. Freezing point
depression Where = , , and Kf=cryoscopic constant

4. Osmotic
pressure =
Minimum pressure
required to prevent Where M = molarity, R = gas constant and T = absolute temperature
osmosis
Physical Chemistry 2

F R E E E N E R G Y A N D E Q U I L I B R I U M
C H E M I C A L E Q U I L I B R I A
S O L U T I O N S O F N O N E L E C T R O L Y T E S

S O L U T I O N S O F E L E C T R O L Y T E S
E L E C T R O C H E M I C A L C E L L S
SOLUTIONS OF ELECTROLYTES

Electrolytes are solutions which conducts electricity to a


greater or lesser extent when substances, particularly salts
and inorganic acids and bases, were dissolved in water or
other appropriate solvents and increasing thereby the total
number of particles in solution.

Strong Electrolytes
The colligative properties of solutions of strong electrolytes
depend primarily on the number of ions that make up the
electrolyte and the extent of dissociation of the electrolyte.

Weak Electrolytes
Solutions that exhibit only poor conductance and a low
degree of dissociation are called weak electrolytes
Colligative Properties of Electrolytes

There is an increase in the number of particles due to


ionization. To account for this increase, the use of Vant
Hoff factor, i, in the equations above is required.
The extent of dissociation of the electrolyte is given
by the Vant Hoff factor, i, which is defined as the ratio of
the colligative effect produced by a concentration m of
electrolyte divided by the effect observed for the same
concentration of non-electrolyte.

= = = =
0 0 0
0
Colligative Properties of Electrolytes

Colligative Property Strong Electrolytes



= (1 )
1. Vapor-pressure lowering +

, = , +
2. Boiling point elevation
, = ,
3. Freezing point depression

4.Osmotic pressure
Minimum pressure required to = ln
, +
prevent osmosis
The Arrhenius Theory
of Electrolytic Dissociation

In 1887, Svante Arrhenius proposed his celebrated Theory


of Dissociation which stated that electrolytes in the solution
are dissociated into electrically charged particles called ions,
in such a manner that the total charge on the positive ions
equal to the total charge in the negative ions.
The net result is, therefore, that the solution as a whole is
neutral in spite of the presence of electrically charged
particles in it.
Vant Hoff factor is related to the degree if dissociation ()
of the electrolyte.
1
=
1
Where v=number of ions formed upon dissociation of one
molecule of the electrolyte
Exercise

1. A 0.01 molal solution of K3Fe(CN)6 at -0.062C.


What is the apparent percentage of dissociation?
Criticism of the Arrhenius Theory

Some theoretical considerations have led to the


conclusion that the Arrhenius theory, although
essentially valid for weak electrolytes, does not
represent the true situation in solutions of strong
electrolytes.
The consensus is that solutions of strong electrolytes
are completely ionized even at moderate
concentrations, and that the s calculated for strong
electrolytes merely give an indication of the
interionic forces of attraction operation in such
solutions.
The Debye-Huckel Theory
of Interionic Attraction

In 1923, P. Debye and E. Hckel published a theory


of interionic attraction in dilute solutions of
electrolytes, which occupies a dominant position
in all considerations involving electrolytes and their
kinetic and thermodynamic behavior.
In Debye-Huckel Theory, the effect of concentration
of the ions enters through a quantity called the ionic
strength of the solution.
This quantity is a measure of the electrical
environment in solution and plays this theory a role
analogous to concentration in the Arrhenius theory.
The Debye-Huckel Theory
of Interionic Attraction
1
= 1 12 + 2 22 + 3 32 +
2
1
= 2
Where 2
= ionic strength if the solution
C1, C2, C3= concentrations of various ions in gram ionic
weights per liter
z1, z2, z3= valences of the respective ions

Values for i for dilute solutions of strong electrolytes at


0C should be given by the relation

= [ . + ]
Exercises

1. Calculate the ionic strength of a solution containing


C=0.10 potassium chloride in the presence of
C=0.01 barium chloride. Also calculate the values
of i of its species using the Debye-Huckel equation.