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Question: a. Which of the monosubstituted cyclohexanes in Table 3.9 on p. 128 has a negative 鈭咷掳 for the conversion of an axial-substituted chair conformer to an equatorial-substituted chair conformer?

b.Which monosubstituted cyclohexane has the most negative 鈭咷掳 for this conversion?

c. Which monosubstituted cyclohexane has the greatest preference for an equatorial position?

d. Calculate 鈭咷掳 for the conversion of 鈥渁xial鈥 methylcyclohexane to 鈥渆quatorial鈥 methylcyclohexane at 25 掳C.

Short Answer

Expert verified
  1. All of the equilibria have negative 鈭咷掳 values for the conversion of an axial-substituted chair conformer to an equatorial-substituted chair conformer.
  2. Tert-butylcyclohexane
  3. Tert-butylcyclohexane
  4. 鈭咷掳=-1.7 kcal/mol

Step by step solution

01

Step 1

For the conversion of an axial-substituted chair conformer to an equatorial-substituted chair conformer, we must identify the monosubstituted cyclohexanes with a negative 鈭咷掳.

The relationship between the equilibrium constant (Keq) and the change in free energy (G) is well understood:

Go = _RT ln Keq

and, Keq=

The Keq value is greater than 1 for all -Govalues. The equilibrium constants for all monosubstituted cycloalkanes except H are larger than 1, as seen in the table.

As a result, for the conversion of an axial-substituted chair conformer to an equatorial-substituted chair conformer, all monosubstituted cyclohexanes in the table except H have a negative Go.

02

Step 2

b)Tert-butylcyclohexane has the most negative 鈭咷掳 for this conversion.

c)Tert-butylcyclohexane has the greatest preference for an equatorial position.

03

 d) Calculation of 鈭咷° for the conversion of “axial” methylcyclohexane to “equatorial” methylcyclohexane at 25 °C.

Go = _RT ln Keq

Keq= 18

-1.986 脳10-3 kcal/mol 脳298 K 脳 ln 18 (T=藲C+273) = Go

Go = -0.59脳 ln 18 kcal/mol

Go = -0.59脳2.89 kcal/mol

Go = 1.79 kcal/mol

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