Actividad de Aprendizaje 2

Termodinámica de Equilibrio para Reacciones Químicas: un Paso a Paso a partir de

una Estequiometría Particular

Desde el punto de vista termodinámico, sabemos que un sistema se encuentra en estado

de equilibrio si se cumple que la energía de Gibbs tiende a un valor mínimo a presión
y temperatura constantes [(dG)T,P = 0]. Ahora bien, ¿cómo aterrizamos eso a una
reacción química? Evidentemente, hay que pasar del lenguaje de la termodinámica a un
lenguaje en términos estequiométricos y de balances de materia en sistemas reactivos.

En clase, presentamos un desarrollo general que nos llevó a establecer que en el equilibrio:
g 0  RT ln K p
donde, para una mezcla de gases ideales:

g0  i gi0 y K p   pi  i .



i i

siendo gi0 energías de Gibbs en estado estándar (1 bar) de cada especie pura y pi las
presiones parciales de cada especie en la mezcla (en clase utilizamos fracciones molares,
pero en la misma presentación empleada en la sesión se detalla la equivalencia con esta
forma en términos de presiones parciales). Esta ecuación se deduce a partir de un
procedimiento en que gradualmente se transcurre del lenguaje termodinámico al lenguaje
en términos estequiométricos y de balances de materia en sistemas reactivos. Sin embargo,
alternativamente a este camino, ¿por qué no familiarizarnos con un caso que en lugar de
dar por ciertas la ecuación de equilibrio presentada arriba, demuestra cómo llegar a
eso mismo pero a partir de un ejemplo basado en una estequiometría química? De eso
se tratará esta Actividad de Aprendizaje, la cual será individual.

Analizarán, comprenderán y reproducirán cuidadosamente el siguiente artículo, mismo que

se adjunta en este documento:
David, C. W., 1988. An Elementary Discussion of Chemical Equilibrium. Journal of
Chemical Education 65(5), 407-409.
Este interesante artículo, hace uso de los conceptos básicos de balances de materia que ya
hemos visto en nuestro curso y de la definición de energía de Gibbs de especies puras para
desarrollar paso a paso la condición de equilibrio de reacciones químicas usando como
ejemplo la estequiometría para la síntesis de amoníaco.

Como productos de esta actividad: entregarán:

1. La reproducción PASO a PASO del ejemplo presentado, incluyendo los pasos

intermedios de derivación total o por partes no presentados en el artículo, y las
razones por las cuáles desaparecen o aparecen algunos términos al derivar. No se
alarmen si detectan que hay algún detalle de escritura en exponentes o factores de las
ecuaciones del artículo. Esto será para entregar a más tardar el viernes 1 de
septiembre (antes de las 13:00). Subirán un escaneado legible de su libreta o de un
procesador de texto. El único formato válido será PDF (valor 50 %).

2. Las personas que cumplan con el punto 1, responderán una prueba rápida en
nuestra próxima sesión de clase, donde se evaluará su compresión del desarrollo
ejemplificado (¿Por qué usa tal o cual ecuación? ¿De dónde toma cada una de las
ecuaciones que sirven de punto de partida? ¿Cuál es el fundamento termodinámico
del planteamiento general? ¿Por qué desaparece o aparece tal o cuál término? ¿Cómo
es que un término pasa de estar expresado de una forma, a otra forma equivalente?
…etc.). Para esta prueba rápida podrán tener a la mano su desarrollo entregado en el
punto 1 (50 %).
An Elementary Discussion of Chemical Equilibrium
Carl W. David
University of Connecticut, Storrs. CT 06268

The crowning glory of thermodynamics is the understand-
ing that we gain of chemical equilibrium. Without relying on
kinetics, we obtain a sense of why chemical equilihrium is
achieved by having the system follow "time's arrow". The
standard derivation of the equation
each of these compounds will differ from the starting values.
During the process of equilibrating, at some instant of time,
the number of moles of HZwill he nH,, the number of moles of
NZ will he n ~ , and
, the instantaneous number of moles of
NH3 will be nNH,.
If we were to define the extent of reaction (.t)

usually does not explicitly show how G is a minimum as

function of .t. This is because the generality of the original OHz
derivation would be violated if a specific reaction were used. then it takes some thought to realize that this definition
As a result the relationship between eq 1and any minimiza- (except for the sign of 0 is applicable to N2 and NH3 in
tion is obscure.' In Hill2 an example is used that relates the addition to Hz. Thus
minimization to the attainment of equilibrium, hut the ex-
ample involves an equilibrium, I ~ N ,- ~ ' N J
f=
" ~ 1

which is unique and not representative of the complexities of is valid, as is

reactions that do not have equal numbers of moles on both ~ N H :-
, no~~d
sides of the equation. In this discussion, a more difficult f=
reaction is used as the prototype, and extra lines of calculus u ~ ~ I

are included to make the discussion accessible to persons
who can mechanically take partial derivatives.
A simple reaction worth studying, prototypical of almost
all aspects of this subject, is
3 H M + Ndg) 2NH,k)
The Gibbs free energy per mole of the Hz is
while the Gibhs free energy per mole of the NZis
The only problem we have is that if HZand N2 are disappear-
ing, then NH3 is appearing, while if Hq and Nz are appearing,
then NH3 is disappearing. Thus f defined on the right-hand
side of the equilibrium equation (i.e., NH3) is opposite in
(2) sien to t defined on the left-hand side of the eauilihrium
equation (i.e., HZand Nz).
-
Basine our definition of o n the ripht-hand side of the
equation (i.e., on NH3) means reversing the sign of zeta in
the case of Hz and Nz, so that

while, of course, the Gihbs free energy per mole of NH3 is and

At equilihrium, we have a mixture of the three suhstances:

HZ,N2, and NH3. The central question of chemical thermo- We will solve now for nH,, nN,, and nNH,, the instantaneous
dynamics is how much of each substance will be present "at mole numbers of the substances involved in the equilihrium.
equilibrium". We want to phrase this in a way that is both We have
correct and understandable, so we have to distinguish care-
fully between the number of moles of the various suhstances nH2= no,, -
which we actually mix together, the number of moles of each
substance that we measure to he present "at equilihrium",
and the "extent of the reaction". This is because the "extent
of reaction" is a theoretical concept, implying that we could
artificially "shift the reaction". The stoichiometry numhers
of the reaction we are studying, (3, 1, and 2) are found by We need these in order to obtain the Gibbs free energy, not
writing for one mole of these substances, but for any number of
moles of them. Thus, if there are nH, moles of Hz present a t
some instant of time, then (assuming all three substances are
ideal gases so that we can substitute P for the fugacity) we
where U H , is 3, UN, is 1, and U N H ~is 2. If we start with noH2 have (using eq 4):
original moles of HZ, no^, original moles of Nz, and ~ ' N H ,
original moles of NH3, then the actual numbers of moles of G H=~n ~ g ' n *+ ~ H P TP H ~
and similarly
' Castellan. G. W. Physical Chemistry, 3rd ed.; Addisan-Wesley:
Readina. MA. 1983:o 230.
HII(T.~ . ' ~ e c t u &
on Matter& Equilibrium: Benjamin: New York.
1966;p 250.

Volume 65 Number 5 May 1988 407

 What is the Gibhs free energy of the mixture of n ~moles , We define
of Hz, n ~ of* N2 and ~ N H moles
, of NH3? I t is just the sum of
the Gihbs free energy of all three components (using eq 5 ) , AGO = ~NH$'NH~ - UHB'H;,
-u ~ $ o ~ l

Grnkture= GNH, + GH, + G N=~ ~ N H $ ' N H ~ + n ~ & ' ~+,n ~ & ' ~ x so that
+ nNH:RTin PNq + nHIRTIn PH1+ nN,RT lnPNx ,G
,,, = n o ~ H & ++
~R~ T3 1nPNHJ+ n',(gDH2 + R T I n PHJ
+ noN3W,9+ RT l n P N J + TAGo
+ XuNHl In PNH3
- uH2 I n PH1- uN2 I n PNJRT (10)

We now take the derivative of G,iXtu, with respect to f and

obtain

Notice that GmiXt.,. is both an explicit and an implicit

function of {. This is because you can see {(explicitly), and i t
is also present in hidden form, hidden in the various partial
pressures, that is,
n;
Pi = *;P,,,.] = -P,l (7)
nto+A

for each of the three components, ni contains {through the

expression
ni = noi f fuj

where the i requires us to choose the appropriate sign. For

nwt.l we have
Continuing, using eq 7, we have derivada de un
nml = ~ ' N H , + ~ U N H : , f nSH2- fuH3 + n ' ~ l- @N1
cociente
se reordena como:

which becomes que se convierte en:

= noNH,, + noHl+ noN2+ fAu
with A u being -2 in our particular case! Defining not.,~las
+ +
~ " N H , n ' ~ , n ' ~ , we have

n,,,.~ = nDb,1 + f A u where we have held the total pressure constant during the
differentiation process. Following the algebraic trail we have
so that the mole fractions would be

Notice that laooears in both the numerator and the denom-

inator of each mole fraction. and similarly
The central thermodynamic point is that G tends to a
minimum at constant T and P. That must mean that, if we
take the derivative of G,iXt,,, with respect to { (at constant
temperature and total pressure) and set it equal to zero, we
will find what special value of (corresponds to an extremum and
in G ; if we could take the second derivative of G,iXt,,, with
respect to f, we could ascertain whether in fact the extre-
mum was a maximum or a minimum.
Rewriting eq 6 we have so that
Gmixture= ~ ' N H , , ~ N H :+, R T I ~ P N H )+ noH9(gOH2
+ RT I n pH.,) + noNr@ON, + R T InPNJ
+ ~('JNH:~'NH:, - ~ H & ' ~ H ?- UNB'N,)
- UH* I n PH?- ON, In PN,)RT
+ ~GJNH:,In PNH:, (9)

408 Journal of Chemical Education

Wondrously, the last six terms in this expression cancel, and which shows that the partial pressures adjust themselves
we obtain until G,iXt,,, finds its minimum value. When dG,iXt,,./a[ is
zero, all the partial pressures have attained their equilibrium
values and we obtain
A G O = - RT In K,, (16)

Volume 65 Number 5 May 1988 409