The mixture that forms maximum boiling point azeotrope is

(I) CH₃COCH₃ + CS₂

CH₃COCH₃ - CH₃COCH₃(A-A) .....   Dipole-Dipole attractions

CS₂ - CS₂ (B-B)   ......    London dispersion forces

Addition of CS₂ disturbs the Dipole-Dipole attractions between

acetone molecules

A-B interactions are weaker than A-A & B-B interactions

This mix. has higher V.P than expected from Raoult's law

It shows positive deviation

It is a minimum boiling azeotrope

(II) Heptane (A)+ Octane(B)  , form an ideal sol.

Magnitude of A-B interactions are equal to A-A and B-B interactions

V.P of the mix. = P_A+P_B

$\Delta {\mathrm{H}}_{mix}=0; {\mathrm{\Delta V}}_{mix}=0$

It a perticular concentration both A & B boil at same temperature.

It is a constant boiling mix.

(III) Water (A) - HNO₃(B)

HNO₃ ionizes in water so A-B interactions are ion - dipole forces which are stronger

Than A-A (H-bonded forces) and B-B (H-bonded forces) interactions

This mix. has lesser VP than expected from Raoult's law

It shows -ve deviation

It is a maximum boiling azeotrope

(IV) C₂H₅OH(A) - H₂O(B)

C₂H₅OH-C₂H₅OH ....... Inter molecular H-bonding

H₂O-H₂O .......   Inter molecular H-bonding

H₂O-C₂H₅OH ....... Inter molecular H-bonding

Inter molecular H-bonding betweenC₂H₅OH - H₂O

is weaker than inC₂H₅OH-C₂H₅OH and  H₂O-H₂O

VP of C₂H₅OH - H₂O is higher than expected

This Azeotropic mix. shows positive deviation from Raoult's law

VP is higher than expected its BP will be lesser than expected

BP of C₂H₅OH - H₂O is lesser than that of  any one of its components.

It is a minimum boiling azeotrpe