The Chemistry Maths Book, Second Edition

(Grace) #1

610 Chapter 21Probability and statistics


systems at very low temperatures and, for example, for the description of the properties


of the conduction electrons in solids.


0 Exercise 22


Large numbers


EXAMPLE 21.11The number of permutations of 52 different objects (a pack of


cards) is52! 1 ≈ 1 8.1 1 × 110


67

.


The number of objects considered in some applications of combinatorial theory in the


sciences can be very large. For example, we are concerned in statistical thermodynamics


with the possible arrangements of the particles of a mole of substance amongst the


available energy states, so thatn 1 ≈ 110


23

, andn!is about 10


10

25

. The computation and


manipulation of such numbers is simplified by means of Stirling’s approximation


3

(21.25)


where the symbol ~ is read as ‘asymptotically equal to’ and means that the ratio of


the two sides of (21.25) approaches unity asn 1 → 1 ∞. In many cases it isln 1 n!that is


of interest rather thann!itself. Then


(21.26)


Use of this asymptotic formula gives errors of about 12 (12n)inln 1 n!when nis large


(see Example 20.14). When nis large enough, we can put


ln 1 n! 1 ≈ 1 n 1 ln 1 n 1 − 1 n (21.27)


Some values are given in Table 21.6.


Table 21.6 Stirling’s approximation


n ln 1 n! eq.(21.26) n 1 ln 1 n 1 − 1 n ln 1 n! 1 − 1 (n 1 ln 1 n 1 − 1 n)


10 15.104 15.096 13.026 2.078


52 156.361 156.359 153.465 2.896


10


10

2.2 1 × 110


11

2.2 1 × 110


11

12.7


10


23

5.2 1 × 110


24

5.2 1 × 110


24

27.4


lnnnnn!−+∼ ln ln n


1


2


2 π


nn


n


e


n

!








∼ 2 π


3

James Stirling (1692–1770), Scottish mathematician, was, like Cotes and de Moivre, a friend of Newton.


The formula named for him appeared in his Methodus differentialisin 1730 and, also in 1730, in de Moivre’s


Miscellanea analytica.

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