Thursday, August 15, 2019

thermodynamics - Pressure at which graphite and diamond are in equilibrium


I came across this problem :



The standard state Gibbs free energies of formation of C(graphite) and C(diamond) at $T = \pu{298 K}$ are $\pu{0 kJ mol-1}$ and $\pu{2.9 kJ mol-1}$, respectively.


The conversion of graphite [C(graphite)] to diamond [C(diamond)] reduces its volume by $\pu{2e-6 m3 mol-1}$.


If C(graphite) is converted to C(diamond) isothermally at $\pu{T = 298 K}$, the pressure at which C(graphite) is in equilibrium with C(diamond), is


(A) $\pu{14501 bar}$

(B) $\pu{58001 bar}$
(C) $\pu{1450 bar}$
(D) $\pu{29001 bar}$



I applied : $$\Delta G_{(P,T)} =\Delta_f G^{\circ}+\int_{p_1}^{p_2}Vdp$$.


Since the system is at equilibrium,$$ \Delta_f G^{\circ}= -\int_{p_1}^{p_2}Vdp$$


Now I am stuck. I have not been given any relation between Pressure and Volume. Is there any assumption i have to make to solve this integral ?



Answer



For each phase (graphite or diamond) you can write


$$ \mu = \mu^\circ+\int_{P^\circ}^{P} V_mdP $$ at constant T.



We are asked to find the pressure $P=P_{eq}$ at which carbon coexists in the two phases (the Gibbs free energy is equal in both) so that


$$ \mu(diamond) = \mu(graphite)$$


This leads to


$$\Delta \mu^{\circ}=-\int_{P^\circ}^{P_{eq}}\Delta V_mdP$$


and, since $\Delta \mu^{\circ}= \Delta_f G_m^{\circ}$, ultimately to the expression you provided:


$$\Delta_f G_m^{\circ}=-\int_{P^\circ}^{P_{eq}}\Delta V_mdP$$


The approximation you are allowed to make at this point is that the solids are incompressible, such that their $V_m$ are constant with change of pressure. It follows that


$$\Delta_f G_m^{\circ}=-\Delta V_m\int_{P^\circ}^{P_{eq}}dP=-\Delta V_m(P_{eq}-P^\circ)$$


which can be solved for $P_{eq}$:


$$P_{eq}=-\frac{\Delta_f G_m^{\circ}}{\Delta V_m}+P^\circ$$



No comments:

Post a Comment

digital communications - Understanding the Matched Filter

I have a question about matched filtering. Does the matched filter maximise the SNR at the moment of decision only? As far as I understand, ...