Investigate the dependence of pV on V for real gases.

Physical Chemistry
2nd Edition
ISBN:9781133958437
Author:Ball, David W. (david Warren), BAER, Tomas
Publisher:Ball, David W. (david Warren), BAER, Tomas
Chapter1: Gases And The Zeroth Law Of Thermodynamics
Section: Chapter Questions
Problem 1.65E: Determine an expression for V/T p, n in terms of and . Does the sign on the expression make sense...
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Investigate the dependence of pV on V for real gases.

Expert Solution
Step 1

In case of ideal gas product of pressure and volume in isothermal process remains constant as:

Chemistry homework question answer, step 1, image 1

for 1 mole of gas. For real gas the case is different.

 

 

 

Step 2

To Investigate the dependence of pV on V for real gases, write the Vander waal equation as:

Chemistry homework question answer, step 2, image 1

Also written as:

Chemistry homework question answer, step 2, image 2

Figure out the product of pV for relative extrema. So, derivative of pV with respect to V is,

Chemistry homework question answer, step 2, image 3

Equating derivative to zero, gives the critical points as:

Chemistry homework question answer, step 2, image 4

Quadratic equation is obtained whose discriminant is equal to zero.

Chemistry homework question answer, step 2, image 5

 

 

 

Step 3

As discriminant is always positive, a quadratic equation has two roots as given:

Chemistry homework question answer, step 3, image 1

Root 1 with negative sign in numerator has no meaning as V1<b

So pV has extremum at:

Chemistry homework question answer, step 3, image 2

Provided as 1-b/a RT >0, the branches of parabola represents the numerator of derivative which will be directed upwards. So sign of derivative changes from minus to plus when going through root V2. This tells that V2 is minima point of function pV: V2= Vmin.

So when vander waal gas is compressed at constant temperature product pV initially decreases the attain a minimum value of pV min then again rise. First step can be explained by dominating attractive forces between molecules and second with increased contribution of repulsive forces.

 

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ISBN:
9781133958437
Author:
Ball, David W. (david Warren), BAER, Tomas
Publisher:
Wadsworth Cengage Learning,