Tarea 3

1. Obtain the Helmholtz equation µ ¶ µ ¶

  
= 2
    
from µ ∙ µ ¶ ¸¶ µ ∙ µ ¶¸¶
 1    1 
+ = 
        

2. Assume that ∆ changes little with temperature, integrate the Gibbs-Helmholtz equation
µ ¶
 ∆ ∆
=− 2
  

and express ∆f at temperature f in terms of ∆, ∆i and the corresponding temperature i .
3. The variation of Gibbs free energy of a substance with temperature is given by  =  +  +  .
Determine how the entropy and enthalpy of this substance vary with temperature.
4. (a)By minimizing the free energy ∆ () given by

 =   − 00  00 − 0  0 + 

as a function of , obtain the expression

2 cos 
=


for the height of capillary rise due to surface tension. (b)Assume that the contact angle  between
water and glass is nearly zero and calculate the height of water in a capillary of diameter 01 mm.
5. (a)Due to surface tension, the pressure inside a bubble is larger than the pressure outside. Let this
excess pressure be ∆. By equating the work done ∆ due to an infinitesimal increase  in the
radius  to the increase in surface energy  show that ∆ = 2. (b)Calculate the excess pressure
inside water bubbles of radius 10 mm and 10 m.
6. For an ideal gas obtain the explicit expressions for the following:
(i)  (   ) =  −   as a function of  ,  and  .
(ii)  =  −   +  as a function of ,  and  .
(iii ) Use the relation  = ( ) and obtain an expression for  as a function of the mole number
density  and  . Also show that  = 0 ( ) +  ln  in which 0 ( ) is a function of  .
7. (a)Obtain a general expression for the entropy of mixing of two non-identical gases of equal molar
densities  , with mole numbers 1 and 2 , initially occupying volumes 1 and 2 . Also show that
the entropy of mixing can be written as ∆mix = − (1 ln 1 + 2 ln 2 ), where 1 and 2 are the
mole fractions and  is the total number of moles.
(b)Using Stirling’s approximation ln  ! ≈  ln  −  , obtain

∆mix =  ln mix = −  (1 + 2 ) (1 ln 1 + 2 ln 2 )

from
( 1 +  2 )!
mix = 
( 1 )! ( 2 )!

1
8. Using the van der Waals equation write the pressure as a function of the density  . Assume that
the quantity  is small and use the expansion
1
= 1 +  + 2 + 3 · · · 
1−

valid for   1, to obtain an equation similar to the virial equation

" µ ¶2 #
  
 =  1 + ( ) + ( ) + ··· 
  

Comparing the two series expansions for  show that van der Waals constants  and  and the virial
coefficients ( ) and ( ) are related by:

 =− and  = 2 


9. Using the relation µ ¶


=
 

show that for a van der Waals gas

µ ¶
 1
(  ) = (0 − 2) + + 
 1 − 
∙ µ ¶¸

− 0 +  ln  −  ln
1 − 

in which  =  .