The protein lysozyme unfolds at a transition temperature of 75.5°C, and the standard enthalpy of transition is 509 kJ mol-1. Calculate the entropy of unfolding of lysozyme at 25.0°C, given that the difference in the constant-pressure heat capacities upon unfolding is 6.28 kJ K-1 mol-1 and can be assumed to be independent of temperature. Hint: Imagine that the transition at 25.0°C occurs in three steps: (i) heating of the folded protein from 25.0°C to the transition temperature, (ii) unfolding at the transition temperature, and (iii) cooling of the unfolded protein to 25.0°C. Because the entropy is a state function, the entropy change at 25.0°C is equal to the sum of the entropy changes of the steps.

0.4774 KJ/K.mol

Explanation:

We are told that the transition at 25.0°C occurs in three steps. Steps i, ii and iii.

Thus;

the entropy of unfolding of lysozyme = ΔS_i + ΔS_ii + ΔS_iii

Now,

C_p,m(unfolded protein) = C_p,m(folded protein) + 6.28 kJ/K.mol

Now, for the first process, ΔS_i is given as;

ΔS_i = C_p,m × In(T2/T1)

We are given;

T1 = 25°C = 25 + 273.15K = 298.15 K

T2 = 75.5°C = 75.5 + 273.15 K=348.65 K

Thus;

ΔS_i = C_p,m × In(348.65/298.15)

Now, for the third process, ΔS_iii is given as;

ΔS_iii = (C_p,m + 6.28 kJ/K.mol) × In(T1/T2)

Thus;

ΔS_iii = (C_p,m + 6.28 kJ/K.mol) × In(298.15/348.65)

Now, we don't know C_pm. So, we have to find a way to eliminate it. We will do it by rewriting In(298.15/348.65) in such a way that when ΔS_iii is added to ΔS_i, C_p,m will cancel out. Thus;

In(298.15/348.65) can also be written as;

In(348.65/298.15)^(-1) or

- In(348.65/298.15)

Thus;

ΔS_iii = - [(C_p,m + 6.28 kJ/K.mol) × In(298.15/348.65)]

Now, let's add ΔS_iii to ΔS_i to get;

ΔS_i + ΔS_iii = [C_p,m × In(348.65/298.15)] + [(-C_p,m - 6.28 kJ/K.mol) × In(348.65/298.15)]

ΔS_i + ΔS_iii = [C_p,m × In(348.65/298.15)] - [C_p,m × In(348.65/298.15)] - [6.28In(348.65/298.15)]

First 2 terms will cancel out to give;

ΔS_i + ΔS_iii = -6.28In(348.65/298.15)

ΔS_i + ΔS_iii = -0.9826 KJ/K.mol

Now,for process ii;

ΔS_ii = standard enthalpy of transition/Transition Temperature

Thus;

ΔS_ii = (509 KJ/K.mol)/348.65

ΔS_ii = 1.46 KJ/K.mol

Thus;

the entropy of unfolding of lysozyme = ΔS_i + ΔS_ii + ΔS_iii = -0.9826 + 1.46 = 0.4774 KJ/K.mol

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