24. Differentiate between physio-sorption and chemi-sorption?

PHYSICAL ADSORPTION CHEMISORPTIONS

The forces operating in these are The forces operating in these cases are
weak vander Waal’s forces. similar to those of a chemical bond.
The heat of adsorption are low i.e. about The heat of adsorption are high i.e. about
20 – 40 kJ mol-1 40 – 400 kJ mol-1
No compound formation takes place in Surface compounds are formed.
these cases.
The process is reversible i.e. desorption The process is irreversible. Efforts to free
of the gas occurs by increasing the the adsorbed gas give some definite
temperature or decreasing the pressure. compound.
It does not require any activation It requires any activation energy.
energy.
This type of adsorption decreases with This type of adsorption first increases with
increase of temperature. increase of temperature. The effect is
called activated adsorption.
It is not specific in nature i.e. all gases It is specific in nature and occurs only
are adsorbed on all solids to some when there is some possibility of
extent. compound formation between the gas
being adsorbed and the solid adsorbent.
The amount of the gas adsorbed is There is no such correlation exists.
related to the ease of liquefaction of the
gas.
It forms multimolecular layer. It forms unimolecular layer.

25. Discuss various factors which control the adsorption process?

Nature of Adsorbent The physico-chemical nature of the adsorbent is
important. Adsorbents differ in their specific surface area and affinity for adsorbate.
Adsorption capacity is directly proportional to the exposed surface. For the non-
porous adsorbents, the adsorption capacity is inversely proportional to the particle
diameter whereas for porous material it is practically independent of particle size.
However, for porous substances particle size affects the rate of adsorption. For
substances like granular activated carbon, the breaking of large particles to form
smaller ones open up previously sealed channels making more surface accessible
to adsorbent.
pH of Solution The surface charge as well as the degree of ionization is
affected by the pH of the solution. Since the hydrogen and hydroxyl ions adsorbed
readily on the adsorbent surface, the adsorption of other molecules and ions is
affected by pH. It is a common observation that a surface adsorbs anions favorably
at low pH and cations in high pH range.
Contact Time In physical adsorption most of the adsorbate species are
adsorbed within a short interval of contact time. However, strong chemical binding
of adsorbate with adsorbent requires a longer contact time for the attainment of
equilibrium. Available adsorption results reveal that the uptake of adsorbate species
is fast at the initial stages of the contact period, and thereafter, it becomes slower
near the equilibrium. In between these two stages of the uptake, the rate of
adsorption is found to be nearly constant. This may be due to the fact that a large
number of active surface sites are available for adsorption at initial stages and the
rate of adsorption is a function of available vacant site. Concentration of available
vacant sites decreases and there is repulsion between solute molecules thereby
reducing the adsorption rate.
Initial Concentration of Adsorbate A given mass of adsorbent can adsorb
only a fixed amount of adsorbate. So the initial concentration of adsorbate solution
is very important. The amount adsorbed decreases with increasing adsorbate
concentration as the resistance to the uptake of solute from solution of adsorbate
decreases with increasing solute concentration. The rate of adsorption is increased
because of the increasing driving force.
Temperature Temperature dependence of adsorption is of complex nature.
Adsorption processes are generally exothermic in nature and the extent and rate of
adsorption in most cases decreases with increasing temperature. This trend may be
explained on the basis of rapid increase in the rate of desorption or alternatively
explained on the basis of Le-Chatelier's principle.
26. Define the electrochemical treatment (ECT) process? Discuss about the
factors which affect the ECT Process?
An ECT unit consists of anodes and cathodes in parallel mode. When
electric power is applied from a power source, the anode material gets oxidized and
the cathode is subjected to reduction of elemental metals and due to further
reactions depending on conditions applied, removal of various pollutants takes
place by EC and/or EF and/or EO mechanisms.
Current density (J), electrolysis time (t) and anodic dissolution:
Faraday’s law describes the relationship between current density (J) and the amount
of anode material that dissolves in the solution.
pH: The initial pH (pHi) of the wastewater will have a significant impact
on the efficiency of the ECT. The effects of pHi on the ECT of wastewater can be
reflected by the solubility of metal hydroxides. The effluent pH after ECT would
increase. The incremental increase in pH with an incremental increase in the amount
of current applied tends to decrease at higher current
Conductivity and the effect of salts: Feed conductivity is an important
parameter in ECT, since it directly affects the energy consumed per unit mass of
pollutants removed. If conductivity is low, higher amount of energy is consumed
per unit of mass of pollutants removed and vice versa. Due to this, some salts
(commonly NaCl) are added to increase the conductivity of feed.