December 22, 2024, 11:41:32 AM
Forum Rules: Read This Before Posting


Topic: Variation principle, secular equation..  (Read 3411 times)

0 Members and 1 Guest are viewing this topic.

Offline emissivity

  • Regular Member
  • ***
  • Posts: 26
  • Mole Snacks: +1/-4
Variation principle, secular equation..
« on: November 22, 2012, 05:29:47 AM »
maybe you can see the picture.

I just want to derive the secular equation.

So I've got the energy equation and

I used the fact that its partial derivatives are 0.

but I don't know why there is ''S'' and ''E''

and why its denominator is not square.



please help me..

otherwise, I just have to memorize the secular equation..




ahhhh
these are the problems from '''''Atkins' physical chemistry 9th ed, peter atkins, oxford, p390~391''''

Offline Schrödinger

  • Chemist
  • Sr. Member
  • *
  • Posts: 1162
  • Mole Snacks: +138/-98
  • Gender: Male
Re: Variation principle, secular equation..
« Reply #1 on: November 22, 2012, 02:58:36 PM »
Instead of applying the u/v rule, try taking the denominator to the left hand side and use the u.v rule. This is easier
"Destiny is not a matter of chance; but a matter of choice. It is not a thing to be waited for; it is a thing to be achieved."
- William Jennings Bryan

Offline juanrga

  • Full Member
  • ****
  • Posts: 231
  • Mole Snacks: +16/-11
    • juanrga - sharing unified knowledge in pure and applied sciences
Re: Variation principle, secular equation..
« Reply #2 on: November 23, 2012, 01:31:47 PM »
Setting
$$E = \frac{U}{V}$$
the partial derivative is
$$\frac{\partial E}{ \partial c_A} = \frac{1}{V} \frac{\partial U}{ \partial c_A} - \frac{U}{V^2} \frac{\partial V}{ \partial c_A}$$
Differentiating the numerator ##U## we obtain ##2 c_A \alpha_A + 2 c_B \beta## and both terms are found in the answer but are not found in your attempt. I do not know what you really did.
Sharing unified knowledge in pure and applied sciences

Offline emissivity

  • Regular Member
  • ***
  • Posts: 26
  • Mole Snacks: +1/-4
Thank you ''Schrödinger''
« Reply #3 on: November 24, 2012, 08:12:23 AM »
your comment is really helpful.

I made it!



dear Juanrga,

thanks for your comment,
but I think Schrodinger's way is easier..

thank you!

Offline juanrga

  • Full Member
  • ****
  • Posts: 231
  • Mole Snacks: +16/-11
    • juanrga - sharing unified knowledge in pure and applied sciences
Re: Variation principle, secular equation..
« Reply #4 on: November 25, 2012, 08:46:44 AM »
No problem you would select the answer that better suit your needs and tastes. Let me show why I think that my method is easy

The above expression for the derivative of a fraction ##E=U/V## can be written in the equivalent form
$$\frac{\partial E}{ \partial c_A} = \frac{1}{V} \left( \frac{\partial U}{ \partial c_A} - E \frac{\partial V}{ \partial c_A} \right)$$
Differentiating the numerator
$$\frac{\partial U}{ \partial c_A} = 2 c_A \alpha_A + 2 c_B \beta$$
Differentiating the denominator
$$\frac{\partial V}{ \partial c_A} = 2 c_A + 2 c_B S$$
Substituting
$$\frac{\partial E}{ \partial c_A} = \frac{2 (c_A \alpha_A + c_B \beta - c_A E - c_B SE)}{V}$$
which is exactly the answer in the textbook.

In my opinion this method is not more complex than moving the denominator in the original fraction to the left hand side, next use the u·v rule, later move the E part to the right hand side, and finally divide both left and right hand sides by the original denominator; but others can disagree of course!
« Last Edit: November 25, 2012, 09:01:02 AM by juanrga »
Sharing unified knowledge in pure and applied sciences

Sponsored Links