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Thursday, April 14, 2022

Ellingham Diagram and it's features:


The changes in Gibbs energy that occur when one moleofoxygen isused may be plotted against temperature for a number of reaction of metals to form
their oxides. Such a graph is shown in Figure below and is called an Ellingham diagram for oxides. Similarly, we can plot Ellingham diagrams for halides.
The Ellingham diagram for oxides show the following important features :
(1) Ellingham diagram normallyconsist of plots of dfG° vs T for the formation of oxides of elements, i.e. for the reaction.
(2) The graphs for metal oxide all slope upwards because the change in Gibbs energybecomes less negative with increase in temperature.
(3) Each plot follows a straight line unless there is some change in phase.
(4) When the temperature is increased, a point will be reached when the line crosses dG = 0 line. Below this temperature the dfG° of oxide is negative and hence the oxide is stable.Above this temperature dfG° of the oxide is positive and hence the oxide becomes unstable and decomposes on its own into metal and oxygen.

Hall Heroult process : Electrolytic refining of Alumina ore of Aluminium:

Electrolysis of fused Alumina.
Cathode : Iron-tank lined with carbon bricks
Anode : carbon
Electrolyte : Molten [Al2O3
(5%) Na3AlF6 (85%) + CaF2 (5%) + AlF3 (5%) ]
O2 is liberated at anode and Al collects at the bottom.


Hoope’s refining process used for electrolytic refining of Aluminium:

Cathode : carbon electrodes
Anode : Fe tank lined with carbon bricks
Electrolyte : Na3AlF6 + BaF2
Bottom layer : Impure aluminium consists of Cu, Si etc in molten state.
Middle layer : molten mixtureof Fluorides of Na, Ba,Al andAl2O3
Top layer : pure molten aluminium.
On passing the current, Al is deposited at cathode from the middle layer and an equivalent amount of Al from the bottom layer moves into the middle layer leaving behind the impurities.

Chemical refining methods:

Wednesday, April 13, 2022

Is oxalate (C2O4)2- Weak field ligand or strong field ?


Although [Fe(CN)6]4- is more stable (EAN-36) than [Fe(CN)6]3-(EAN-35) as par EAN rule but actually [Fe(CN)6]3 is more stable than [Fe(CN)6]4- ?

Although [Fe(CN)6]4- is more stable (EAN-36) than [Fe(CN)6]3-(EAN-35) as par EAN rule but actually  [Fe(CN)6]3 is more stable than  [Fe(CN)6]4- because in  Fe+3  Zeff will be more hence bonding between Fe+3 and -CN is more effective.