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Lectura Fisicoquimica
Lectura Fisicoquimica
Lectura Fisicoquimica
20140248
Educação
Ana Quílez-Díaz and Juan Quílez-Pardo*
IES Benicalap, Departamento de Física y Química, Nicasio Benlloch, 46015 Valencia, Spain
This paper summarizes the misrepresentations related to Gibbs energy in general chemistry textbooks. These misrepresentations
arise from a problem in the terminology textbooks use. Thus, after reviewing the proper definition of each of the terms analyzed, we
present two problems to exemplify the correct treatment of the quantities involved, which may help in the discussion and clarification
of the misleading conventions and assumptions reported in this study.
Thus, the sign of DrG allows us to predict the direction of the where, Kº is the thermodynamic equilibrium constant. For a given
spontaneous chemical reaction. Moreover, if DrG = 0, the equilibrium equilibrium reaction such as: a A(g) + b B(g) r R(g) + s S(g),
has been attained. it is expressed as follows,
DG is a finite difference in the Gibbs energy between two states.
That is,
These final and initial states can even be the equilibrium situation
or reactants or products. For example,
and Q is the reaction quotient, which has the form of the equilibrium
DG = Geq – Greactants and DG = Geq – Gproducts (7) constant, Kº, but it is not equal to the equilibrium constant [observe
that when DrG = 0 (equilibrium), then Q = Kº],
Notice that in both cases DG ≠ 0.
DGº is also a finite difference, but now DGº is the difference in the
Gibbs energies of the products and reactants when they are unmixed
and each is in its standard state, (13)
(8)
It should be noticed that DrG ≠ DG. Not only is there a con- Kº and Q are here defined for homogeneous gas phase reactions.
ceptual distinction between these two quantities, but there is also a Notice that equation (13) contains non-equilibrium specification of
differentiation in the units used to measure each quantity. That is, partial pressures, while the thermodynamic equilibrium constant, Kº,
one should realise that DG is an extensive quantity; it is expressed defined in equation (12) contains equilibrium specifications.
in energy units only, kJ. Conversely, DrG is not a finite difference: it As DrGo = –RT ln Kº, equation (11) can be written as follows
is an instantaneous rate of change of G with respect to the extent of
reaction. It is an intensive quantity and is normally reported in units DrG = DrG0 + RT ln Q (14)
of kJ mol-1. At equilibrium the rate of Gibbs energy change is zero,
DrG = 0. But, the value of DG is indeed a finite diference between a Equation (14) allows us to calculate the value of DrG and, the-
given initial situation and a final one that can be the equilibrium state. refore, to discuss the direction of the spontaneous reaction. At this
That is, as the process goes from the initial mixture to equilibrium a point the reader is reminded that the forward reaction is spontaneous
change in Gibbs energy occurs, thus DG ≠ 0. However, it is true that when DrG < 0 and for the reaction to reverse spontaneously DrG > 0.
some authors may state their readers that the initial situation is already This has been the approach performed in the two examples below.
equilibrium. Hence, then, obviously, DG = 0, since the process will But, one does not need to calculate the value of DrG in order to
have done nothing to get to equilibrium. know the direction of the spontaneous reaction. Q-K inequalities can
The standard free energy of reaction, DrGº, is the rate of change be used as a basic criteria for spontaneity in isothermal conditions.
of standard Gibbs energy, viz. From equation (11) we can state that if Q < Kº (DrG < 0), the forward
reaction is spontaneus; conversely, if Q > Kº (DrG > 0), the reaction is
(9) spontaneus in the backward direction. Eventually, if Q = Kº (DrG = 0),
there is an equilibrium mixture. In example 1 we have calculated the
value of DrG corresponding to an initial non-equilibrium situation.
It is a constant quantity, As DrG < 0, we have concluded that the reaction will proceed in
the forward direction. We could have reached the same conclusion
(10) stating that in that initial conditions, Q < Kº. And in example 2, the
equilibrium disturbance has caused that DrG > 0, concluding that
the reaction will proceed in the backward direction. Similarly, we
[In eq. (10) we have considered that initially we have n0(A) = a mol could have reached the same conclusion stating that in that disturbed
and n0(B) = b mol; thus, ξinitial = 0 and ξmax = 1] equilibrium conditions, Q > Kº.
Therefore, DrGº is an intensive quantity and is expressed in kJ Finally, it should be stressed that only when Q = 1 can the sign
mol-1. of DrGº serve to predict the direction of the spontaneous chemical
Textbook discussions concerning the meaning of the value of this reaction, as in this situation DrG = DrGº.
last quantity are usually made with incorrect analyses. That is, neither Table 1 summarizes the Gibbs energy (G) terminology associa-
can the negative value of DrGº be used as the general condition for ted with the four quantities (DrG, DG, DrGº and DGº) that have been
spontaneity, nor is it true that a positive value of DrGº means that a discussed previously. It should be stressed that DrG ≠ DG. DG is an
chemical reaction will not proceed. It is the sign of DrG that should extensive quantity; its value is indeed a finite diference between a
always be considered for that purpose. In example 1 we analyse this given initial situation and a final one. Conversely, DrG is not a finite
situation. In this case, despite DrGº > 0, the forward reaction is spon- difference: it is an instantaneous rate of change of G with respect to
taneous (DrG < 0). We will make an enlarged point of clarification on the extent of reaction. It is an intensive quantity and can be calcula-
this issue after discussing the meaning of equation (14). ted using an equation that has two terms: one is the value of DrGº,
A proper calculation of DrG makes use of the following equation which is constant, and the second one depends on the value of the
reaction quocient, Q . At this point, it should also be emphasised that
(11) the value of DrG changes as the composition of the reaction mixture
varies, which means that the value of Q is modified. But the value
Vol. 38, No. 1 Avoiding first-year university chemistry textbooks’ misrepresentations in the teaching of spontaneous reactions 153
In the study of this reaction, the total pressure of the gas mixture
is 500 bar at 600 K, and the amounts of each substance are:
n(CO) = 1.64 mol, n(H2) = 0.82 mol and n(CH3OH) = 0.95 mol.
Standard free energy of reaction (intensive quantity; kJ mol-1 units): State the direction of the spontaneous reaction.
basic role. That is, one merely needs to distinguish between the ratio
Example 2 of partial pressures or concentrations at the disturbed equilibrium
At 700 K, ΔrGº = 23.4 kJ/mol, for the equilibrium corresponding situation (Q) and the value when the system is at equilibrium (K).
to the ammonia synthesis: In example 2, as Q > Kº the backward reaction is then spontaneous.
Although similar exercises as examples 1 and 2 can be found
1/2 N2 (g) + 3/2 H2 (g) NH3 (g) in some first-year chemistry textbooks, in most of the cases studied
their authors have not paid attention to the basis of the above discus-
In the study of this reaction, the total pressure of the gas mixture is sion, which has caused several misrepresentations and misleading
100 bar at 700 K, and the equilibrium amounts of each substance assumptions. In summary, the sign of DrGº must not be used as a
are: n(N2) = 0.513 mol, n(H2) = 0.204 mol and n(NH3) = 0.139 general condition in order to predict the direction of a spontaneous
mol. If it is added, at constant temperature and pressure, 0.120 mol reaction; it is the sign of DrG that should always be interpreted in
of N2(g), which will be the direction of the spontaneous reaction? order to accurately predict the direction of the spontaneous reaction
when giving a situation involving some initial conditions. The same is
Solution true when studying the evolution of a disturbed chemical equilibrium
Although this is a case of a disturbed equilibrium, its treatment system. That is, Le Châtelier’s principle is a limited rule that can be
is similar to the example 1. The aim is to calculate ΔrG after dis- overcome analysing the meaning Q-K inequalities, which are ground-
turbing the initial equilibrium. If DrG < 0, the forward reaction ed on the meaning of the sign of DrG. Textbooks usually concentrate
[1/2 N2 (g) + 3/2 H2 (g)→ NH3 (g)] is spontaneous. Conversely, if on practical situations where the addition of one of the reactants is
DrG > 0, the backward reaction [NH3 (g) → 1/2 N2 (g) + 3/2 H2 (g)] assumed at constant volume. Example 2 studies the evolution of a
is then spontaneous. disturbed chemical equilibrium in which a reactant has been added
The value of DrG can be determined as follows at constant presssure. The presentation of new possible perturbed
situations in which the addition of one of the reactants is made at
ΔrG = ΔrG0 + RT ln Q constant pressure may contribute in overcoming some student (and
also teacher) misconceptions connected with this topic.
As we know the value of DrGº, we need to calculate the value of Q.
CONCLUSIONS
The reaction quotient, Q, is
The presentation of Gibbs energy accomplished in this paper
(pº = 1 bar) assists in establishing the fundamentals to make alternative accu-
rate approaches to the current misrepresentations found in general
chemistry textbooks.12,13 This paper has focused on the appropriate
where calculation of both DrG and DrGº and on the meaning of their sign. To
accomplish this purpose, the examples examined in this study were
designed on the proper use of free energy of reaction in the analysis of
spontaneous reactions. It is stressed that the calculation (and then the
sign) of DrG serves to establish the direction of a chemical reaction.
Clarification in the meaning of the different terms involved seems
essential, which provides sound approaches when dealing with spon-
taneous reactions. Two problematic cases have been analysed on the
basis of current misrepresentations and misconceptions. It has been
emphasized that: a) the sign of DrGº must not be used as a general con-
dition in order to predict the direction of a spontaneous reaction and
Thus, we have b) adding a reactant to a chemical equilibrium mixture at contant
pressure is a case in which the Le Châtelier’s principle is a limited
rule that can be overcome analysing the meaning of Q-K inequalities
(which are grounded on the meaning of the sign of DrG) in order to
make accurate predictions.
Finally, Hence, similar problems to the ones discussed in this study can be
ΔrG = ΔrG0 + RT ln Q presented to students when dealing with spontaneous reactions. This
ΔrG = 23.4 ×103 J mol-1 + (8.3145 J K-1 mol-1)(700 K)(ln 1.84×10‑2) may help instructors in avoiding both current misrepresentations of
= 146 J mol-1. Gibbs energy and the misuse of Le Châtelier’s principle.
As DrG > 0, the the backward reaction [NH3 (g) → 1/2 N2 (g) +
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