BirgeSponer plots are generally made using G for n values far from the dissociation limit. If the

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Birge–Sponer plots are generally made using ΔG for n values far from the dissociation limit. If the data include n values close to the dissociation limit, deviations from a linear relationship between ΔG and n + 1/2 are observed. Taking these deviations into account allows a more accurate determination of the n value corresponding to dissociation and D0 to be made. A student determined the following values for ΔG versus n for the ground state of H2:

n………………………………………. ΔG (cm−1)

0………………………………………. 4133

1………………………………………. 3933

2………………………………………. 3733

3………………………………………. 3533

4………………………………………. 3233

5………………………………………. 3000

6………………………………………. 2733

7………………………………………. 2533

8………………………………………. 2267

9………………………………………. 2000

10………………………………………. 1733

11………………………………………. 1400

12………………………………………. 1067

13………………………………………. 633

a. Construct a Birge–Sponer plot (ΔG versus n + 1/2) using the above data, and fit the data assuming a linear relationship between ΔG and n. Determine the value of n where ΔG = 0. This is the H2 ground-state vibrational level at dissociation.

b. The area under the Birge–Sponer plot is equal to the dissociation energy, D0. This area is can be determined by summing the ΔG values from n = 0 to n at dissociation [determined in part (a)]. Perform this summation to determine D0 for ground state I2. You can also integrate your best-fit expression ΔG (n) from zero to the n value corresponding to dissociation. Compare your result with the value shown in Table 19.3.

c. Determine the value of n where ΔG = 0 and D0, assuming a quadratic relationship between ΔG and n, ΔG = a + b (n + 1/2) + c (n + 1/2)2. Which fit gives better agreement with the value for D0 shown in Table 19.3?

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Physical Chemistry

ISBN: 978-0321812001

3rd edition

Authors: Thomas Engel, Philip Reid

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