c

?


 
? 


       

 

 
 ?








      


 

! 
"
 


      

# 

 



  

# 

$ !



   ! %&'()*)+,! - -- - - -- -
 

 
! 
 





 

^

 



1. To measure the conductivity of solutions of KCl and to establish the dependence of

molar conductivity on concentration.

2. To measure the conductivity of acetic acid solutions and calculate the dissociation
constant of the acid from the data.

 

j
 


  

 
The experimentally measured conductance, G, of a solution is that of a certain volume
of the solution contained between the electrodes of the conductivity cell. (These
electrodes are the thin metal plates that can be seen on the inside of the cell, and must
be completely covered during measurements). The meter actually measures the
resistance, R, of the solution between the electrodes and converts it to conductance.

G=1/R

In order to use this quantity to compare different solutions we introduce another

quantity called specific conductivity, k and
k = G x cell constant

where the cell constant is a quantity describing the geometry of the cell and

cell constant = „/A

where „ is the distance between the electrodes and A is the common electrode area (or
the area of one electrode if both have the same area). The cell constant is not found by
measuring distances but is determined by measuring the conductance of an electrolyte
whose specific conductivity is already known. The molar conductivity,
ȁm = ț / c

w here c is the molar concentration.

Kohlrausch found an empirical expression for the molar conductivity as
ȁm = ȁmo - k ¥c

where ȁmo is the molar conductivity at infinite dilution and 'k' is a constant whose
value depends on the type of electrolyte used (i.e. MA, M2A, MA2, etc.). The refined,
Debye-Onsager theory gives essentially the same result.

Ä4 
  



Consider the dissociation of acetic acid (a weak acid),

Î
Î Î 



  




where Į is the degree of dissociation and c is the initial concentration of the acid
before dissociation. The dissociation constant, K, is given by

K = Į2c / (1- Į)

If this equation is solved for Į, and Į is expressed as the ratio ȁm / ȁmo we get the
following equation

1 / ȁm = 1 / ȁmo + c ȁm/ K(ȁmo)2

which is known as the Ostwalds dilution law, and we can see that, from a plot of 1 /
ȁm against cȁm, the values of ȁmo and K can be obtained from the intercept and slope
respectively.

j  
Conductivity meter and cell, 0.1 M solutions of KCl and acetic acid, beakers, 2
burettes and a graduated pipette.

X 
Switch on the conductivity meter. Familiarize yourself with the controls on the front
panel. From the stock solutions m

m

to prepare 50 cm3 of the following
dilutions for each electrolyte: 0.0500, 0.0400, 0.0300, 0.0200 and 0.0100 M. Use one
burette for the stock solution and ones for the distilled water. Rinse the conductivity
cell thoroughly in distilled water, drain off the excess water and dip it into the solution
whose conductance you wish to determine, taking care that the electrodes are
completely immersed in the solution. Connect the cell leads to the terminals marked
cell on the meter. Set the range switch to the highest value and observe the reading on
the meter. If you do not observe any movement on the meter (no movement of the
needle), move to the next range, and so on. The reading on the meter multiplied by the
range is the conductance value. Measure the conductance of all the solutions that you
have prepared, beginning with the least concentrated,   

„



m „ 

 „m. From the value of the conductance for 0.1 M KCl,
calculate the cell constant using țKCl = 1.285 x 10-1 S dm-1 (S = siemens = ohm-1) at
25 °C. Using this value for the specific conductivity you can calculate all the other
specific conductivities.

c  

For each electrolyte solution calculate ț and hence ȁm at each concentration. Plot
ȁm vs. ¥c for KCl. Compare your experimental value of ȁmo with that obtained from
the literature.
For acetic acid plot 1/ ȁm against cȁm and determine the value of the dissociation
constant (K). Use the box method to calculate the error in the slope and hence
determine the error in the value of K. Compare your value with the literature value.

Copyright © 2002-2009 by Robert John Lancashire, all rights reserved.

˜


 


 




˜
  
  



˜m ! "

Created Oct 2002. Links checked and/or last modified 19th October 2009.
´

      



Determination of Equilibrium
Unit VII: Equilibrium
(Periods 16)

^

 
  
      
 


      

     


   
      

     
     
    ! "
 
 
 

  

#$ !


%

When a chemical reaction gets started the reactants are present in the initial stage, but as the
reaction proceeds, the concentration of the reactants decreases and that of products increases.
Finally, a stage is reached when no further change in concentration of reactants and products is
observed. This is a common observation that most of the reactions when carried out in closed
vessels do not go to completion under given set of conditions of temperature and pressure.
Such reactions in which only a part of the total amount of the reactants is converted into
products are reversible reactions.
Equilibrium and its Dynamic Nature
The state of reversible reaction at which the concentrations of reactants and products do not
change with time is called a state of chemical equilibrium. This state can be recognized by the
constancy of certain measurable properties such as pressure, density, colour, concentration,
etc. At equilibrium, both the forward and backward reactions are still taking place, but the rates
of the forward and backward reactions become equal. The concentration of each species
become constant and the system is said to be at dynamic equilibrium. It is dynamic because the
movement of mass is at the microscopic level although no apparent change is observed. The
equlilibrium may be established in physical process (physical equilibrium) and in chemical
process (chemical equilibrium).
Equilibrium Involving Physical Changes
Substances exist in three states: solids, liquids and gases. The following types of
equilibriums exist in three states:

Solid-Liquid Equilibrium
When a solid is heated it starts melting at a certain fixed temperature (melting point). At this
stage even when the heating is continued, the temperature does not change until the whole of
solid is converted into liquid. The state when solid and liquid phases of a substance coexist is
called solid-liquid equilibrium. Solid-liquid equilibrium is described as,

Liquid-Gas (vapor) Equilibrium

When a liquid is placed in an open container it disappears completely after some time.
However, when the same liquid is placed in a closed container, even after a long period only a
part of the liquid disappears. The obvious difference is that the vapours of the liquid held in an
open container can escape to the atmosphere, while the vapours in the closed container are
confined to the space above the liquid.
Solid-Vapor Equilibrium
When substances get sublimated,the solid gets converted into vapour without passing
through the liquid phase.Sublimation thus involves solid vapour equilibrium. On cooling
the vapours, the solid is given back. This equilibrium is obtained in closed systems only.
Examples of solid-vapour equilibrium are, camphor, iodine, ammonium chloride etc.
Equilibrium Between a Solid and its Solution
The extent to which a solute dissolves in any solvent is termed as its solubility. Different
substances have different solubility, some dissolve more and some less. A solution containing
the maximum amount of solute at a fixed temperature and pressure is called a saturated
solution. A saturated solution cannot dissolve more solute and the added quantity of solute
merely settles down in the container. At this condition of saturation a dynamic equilibrium exists
between the solid and the solution phases.
Solid substance solution of the substance
Equilibrium Between a Gas and its Solution
Gases can be dissolved in suitable liquids. The solubility of a gas in any liquid depends
upon:
* Nature of the gas and the liquid.
* Temperature of the liquid.
* Pressure of the gas over the surface of the solution.
General Characteristics of Physical Equilibrium
From the physical equilibrium studied above, we have noticed that at equilibrium, some of
the measurable properties of the system become constant.
Equilibrium Involving Chemical Systems
In reversible reactions chemical reactions take place in both the forward and backward
directions. For example, the reaction between gaseous hydrogen and iodine vapours to give
gaseous hydrogen iodide is a reversible reaction and may be expressed as:

Characteristics of Chemical Equilibrium

Chemical equilibrium is dynamic in nature. The constancy of observable property in an
equilibrium system does not mean that the reaction has stopped altogether. After the attainment
of equilibrium the reaction does not stop although, it appears to have been stopped. The rates
of two opposing reactions become equal. This means that if products are formed from the
reactants, exactly equivalent amount of reactants being formed from the products.
Law of Mass Action and Equilibrium Constant
The law of mass action correlates the rate of a chemical reaction and the concentration of
the reactants. C.M. Guldberg and P. Waage (1864-67) suggested this relationship. This law
states that, at a constant temperature and pressure, the rate of a chemical reaction is directly
proportional to the product of the molar concentration of the reactants each raised to a power
equal to the corresponding stoichiometric coefficient, which appears in the balanced chemical
equation.
Rules for Writing Equilibrium Constant Expressions
Expression for the equilibrium constant of a reaction is written in the form of a ratio. The
numerator consists of the molar concentration (or partial pressure) terms of the products each
raised to a power equal to its stoichiometric coefficient in the balanced chemical equation, and
the denominator consists of the molar concentration (or partial pressure) terms of the reactants
each raised to a power equal to the stoichiometric coefficient in the balanced chemical equation.
Units of Equilibrium Constant
In mathematical sense, equilibrium constant is not a constant. It is called constant because
at a fixed temperature and pressure, the value of the equilibrium constant for a reaction is
constant. The unit of equilibrium constant (K) of a reaction depends upon the number of moles
of the reactants and products involved in the reaction.
Characteristics of Equilibrium Constant
The value of the equilibrium constant of a reaction is the same, at constant 'T' and 'P'. However,
if either temperature 'T' or pressure 'P' or both are changed, the value of the equilibrium
constant may also change. For example, the value of Kp (equilibrium constant in terms of partial
pressures) for the reaction,

at 700 K and 800 K are 1.5 x 10-4 and 1.4 x 10-5 respectively.

Reaction Quotient and the Equilibrium Constant

The concentration ratio, i.e., the ratio of the product of concentration of the products to that of
the reactants at any time (t) is known as the concentration quotient 'Q' of the reaction at time (t).
The value of Qc or Qp will be different from the value of Kc or Kp if the reaction is not at
equilibrium.
Predicting the Direction and Extent of Reaction
The magnitude of the equilibrium constant, K of a reaction indicates how far a reaction can
go in the direction as written. The larger the value of K, the greater will be the equilibrium
concentration of the components on the right hand side of the reaction (products) relative to
those on the left hand side (reactants).
Le Chatelier's Principle
The state of equilibrium in any system depends upon factors present in the system, such as
temperature, pressure and concentration of various species. These factors are called reaction
variables or parameters. A change in any one of the parameters may affect the position of the
equilibrium. The general rule that can explain the effect of changes in these parameters on the
state of equilibrium was formulated by H. Le Chatelier (1885), and F. Braun (1886) and is
commonly called as Le Chatelier's principle.
Applications of the Le Chatelier's Principle
The Le Chatelier's principle has a great practical significance for all physical and chemical
systems.