Sunday

March 1, 2015

March 1, 2015

Posted by **esmat** on Monday, June 13, 2011 at 5:35pm.

, molecules contained in a volume V

(0)

. Assume that

there is no correlation between the locations of the molecules (ideal gas). Do not

use the partition function in this problem.

(a) Calculate the probability P (V; N) that an arbitrary region of volume V contains

exactly N molecules.

(b) Calculate the average value N¹

and the standard deviation of N.

(c) Show that if both V and V

(0) ¡ V are large, the function P (V; N) assumes a

Gaussian form for N close to N¹

.

(d) Show that if both V ¿ V

(0)

and N ¿ N(0)

, the function P (V; N) assumes a

Poisson form.

- physics -
**Count Iblis**, Monday, June 13, 2011 at 8:29pmProbability for one molecule to be in that region is

q = V/V0

therefore:

P(V,N) =

N0!/(N! (N0-N)!) q^N (1-q)^(N - N0)

The average number N' is q N0 because the probability q for each molecule to be in the region is independent. You can also find this by direct computation:

N' = Sum from N = 0 to N0 of N P(V,N)

To perform the summation, consider the function

Q(V,N) =

N0!/(N! (N0-N)!) q^N r^(N - N0)

where q and r are considered to be independent variables. Then we can compute the summation by differentiating w.r.t. q while keeping r constant and then we put r = 1-q

So, we have:

N' = f(q,1-q)

where

f(q,r) = Sum from N = 0 to N0 of

q d/dq Q(V,N) =

q d/dq Sum from N = 0 to N0 of Q(V,N) =

q d/dq (q+r)^N0 =

N0 q (q+r)^(N0-1)

We thus have:

N' = f(q,1-q) = N0 q

The standard deviation can be evaluated in a similar way.

<N^2> = g(q,1-q)

with

g(q,r) = q d/dq q d/dq (q+r)^N0 =

N0 q d/dq q (q+r)^(N0-1) =

N0 q (q+r)^(N0-1) +

N0 q^2 (N0-1)(q+r)^(N0-2)

So,

<N^2> = N0 q + N0(N0-1)q^2

<N^2> - <N>^2 =

N0 q + N0(N0-1)q^2 - N0^2 q^2 =

N0 q - N0 q^2 =

N0 q (1-q)

So, the standard deviation is:

sqrt[No q (1-q)]

To derive the Gaussian and Poisson approximation in the appropriate limits, you need to expand

Log(P) using the Stirling approximation for log(N!) for large N. This only involves trivial manipulations.

**Answer this Question**

**Related Questions**

(1-13) Chemistry - Science - Which of the following effects will make the ratio...

physics - Thermal energy is caused by motion of? 1. mixing water molecules ...

Chem - In the van der waals equation, the constants a and b are: 1)used to ...

physics/chemistry - (a) An ideal gas occupies a volume of 1.0 cm3 at 20°C and ...

chemistry - we believed that the molecules of a gas move around fairly rapidly...

Physics - (a) An ideal gas occupies a volume of 1.6-cm3 at 20°C and atmospheric ...

Chemistry. PLEASE HELP - If we believed that the molecules of a gas move around ...

Combinatorics - Entropy 1. Suppose a room has n molecules of a gas. We divide ...

Chemistry - All of the following are postulates of the kinetic molecular theory ...

SCIENCE 1 - The van der waals equation incorporates corrections to the ideal gas...