Energy xxx (2015) 1e21

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Energy
journal homepage: www.elsevier.com/locate/energy

Thermodynamic chemical energy transfer mechanisms of

non-equilibrium, quasi-equilibrium, and equilibrium chemical
reactions
Heui-Seol Roh*
Department of Mechanical Engineering, City College of New York, New York, NY 10031, USA

a r t i c l e i n f o a b s t r a c t

Article history: Chemical energy transfer mechanisms at finite temperature are explored by a chemical energy transfer
Received 22 January 2015 theory which is capable of investigating various chemical mechanisms of non-equilibrium, quasi-equi-
Received in revised form librium, and equilibrium. Gibbs energy fluxes are obtained as a function of chemical potential, time, and
20 May 2015
displacement. Diffusion, convection, internal convection, and internal equilibrium chemical energy fluxes
Accepted 16 June 2015
are demonstrated. The theory reveals that there are chemical energy flux gaps and broken discrete sym-
Available online xxx
metries at the activation chemical potential, time, and displacement. The statistical, thermodynamic theory
is the unification of diffusion and internal convection chemical reactions which reduces to the non-
Keywords:
Thermodynamic chemical energy transfer
equilibrium generalization beyond the quasi-equilibrium theories of migration and diffusion processes.
theory The relationship between kinetic theories of chemical and electrochemical reactions is also explored. The
Chemical non-equilibrium theory is applied to explore non-equilibrium chemical reactions as an illustration. Three variable separa-
Chemical quasi-equilibrium tion constants indicate particle number constants and play key roles in describing the distinct chemical
Chemical equilibrium reaction mechanisms. The kinetics of chemical energy transfer accounts for the four control mechanisms of
Chemical and electrochemical reactions chemical reactions such as activation, concentration, transition, and film chemical reactions.
Four control mechanisms © 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Energy transfer is a central process in the evolution of the uni-
verse, and one distinctive form of energy transfer is chemical energy
transfer. Thermodynamics dealing with energy transfer and chem-
ical energy transfer dealing with chemical reactions have various
application areas in science and engineering. The coupled mecha-
nisms of thermodynamic and chemical reactions are definitely
demanded in diverse fields including phase transition, chemistry,
electrochemistry, corrosion, thermal devices, microscopic organ-
isms, physics, mechanical engineering, biology, and energy.
Extensive research has been conducted for developing a ther-
modynamic theory to describe chemical reaction processes. Exist-
ing theories of chemical kinetics include the Arrhenius equation,
collision theory, potential energy surfaces, Gibbs flux formalism,
Lagrangian formalism, and transition state theory [1e26]. Never-
theless, chemical reaction mechanisms are so complicated that
their entire understanding in terms of existing theories [27e29] is
* Tel.: þ1 212 650 6759; fax: þ1 212 650 8013.
E-mail address: hroh@ccny.cuny.edu.
not possible yet. The kinetics based on the conservation of mass or
concentration provides only the information about the rate of
chemical reactions and the rate constant. Their nominal forms also
depend on the orders of chemical reactions [27e29]. The concen-
tration equation for mass (or particle number) transfer [33] is
useful in investigating particle diffusion:
vC=vt þ va $VC ¼ D0 V2 C þ C0i : (1)
Eq. (1) is closely related to chemical reactions when the internal
generation Ci0 is taken into account. However, the precise form of
the internal convective energy generation is not exactly clarified so
far. The other existing theories for chemical reactions are estab-
lished under the assumption of chemical equilibrium, so they
cannot predict non-equilibrium chemical processes. Otherwise,
they describe chemical reactions under some limited situations. For
example, transition state theory assumes intermediate reaction
states which are described by a statistical formalism, and then they
are combined with the reaction equation, but their detailed dy-
namic properties are not given explicitly [10e12,27]. Therefore, a
robust theory of chemical reactions should provide essential dy-
namic and static information about chemical reactions under a

http://dx.doi.org/10.1016/j.energy.2015.06.049
0360-5442/© 2015 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Roh H-S, Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and
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2 H.-S. Roh / Energy xxx (2015) 1e21

certain fundamental principle. We are here interested in a chemical

energy transfer theory which are simultaneously capable of inte-
grating thermodynamic, spatial, and temporal properties as well as
describing non-equilibrium, quasi-equilibrium, and equilibrium
processes.
An internal energy transfer theory [30] for thermodynamic non-
equilibrium, quasi-equilibrium, and equilibrium has been pro-
posed. The systematically unified transport theory is capable of
producing the three energy transfer mechanisms of thermody-
namics so that it estimates parameters in thermodynamic equi-
librium and non-equilibrium states and clarifies the characteristics
of transport processes [30e36]. The kinetic theory is also applicable Fig. 1. Chemical energy transfer in the hierarchy for energy transfer mechanisms.
to understanding the chemical energy transfer mechanisms in Electrochemical energy transfer is considered as a branch of chemical energy transfer.
various chemical phenomena in nature.
We have furthermore proposed the statistical thermodynamic
theory for electrochemical reactions [31,32] which is vital to chemical energy transfer theory to examine various chemical re-
examine both diffusive and internal convective electrochemical actions to clarify their features. The theory is utilized to examine
reactions. It is a transport theory for electrochemical reactions chemical energy transfer mechanisms in equilibrium, quasi-
leading to the integration of diffusion and internal convection, a equilibrium, and non-equilibrium. The chemical energy transfer
generalization beyond quasi-equilibrium theories for migration theory can be applied to internal convective chemical processes at a
and diffusion, and the unification of internal equilibrium and solideliquid boundary as its demonstration. Chemical energy flux
equilibrium. The Nernst equation is derived from the internal profiles are predicted as a function of chemical potential, time, and
convective and equilibrium processes, the time rate of electro- distance. The four control regimes are also anticipated as a function
chemical reactions is obtained, and the spatial cross section is of chemical potential, time, and distance in analogy with electro-
gained from the kinetic theory. chemical reaction regimes: activation, concentration, transition,
In these contexts, we propose a chemical energy transfer theory and film chemical reaction regimes.
for non-equilibrium, quasi-equilibrium, and equilibrium chemical
energy as a special case of the internal energy transfer theory [30].
2. Internal energy transfer theory
The theory is analogous to the statistical thermodynamic theory for
electrochemical reactions [31,32]. It is able to probe internal
The internal energy transfer theory [30] has been proposed for
convective chemical energy transfer in chemical reactions since it is
the transfer mechanisms of heat, work, and chemical energy. A total
a generalization beyond chemical energy transfer in quasi-
system containing reactants and products is thermodynamically
equilibrium. It is thus a non-equilibrium extension beyond chem-
isolated from its surroundings, and has thermodynamic energy
ical equilibrium and quasi-equilibrium. It is based on the conser-
transfer due to thermal, mechanical, and chemical non-equilibrium
vation of energy rather than the rate of chemical reactions based on
between reactants and products. The local thermodynamic non-
the conservation of mass which the existing theories [27e29]
equilibrium is characterized as the intensive variables of temper-
depend on. The chemical transfer theory provides the chemical
ature, pressure, and chemical potential [37].
potential and spatial dependence in addition to the temporal
dependence of chemical reactions. The theory is likewise compe-
tent to explore both dissociation and synthesis chemical reactions 2.1. Motivation of internal energy transfer
regardless of the molecularity of a chemical reaction.
In the chemical energy transfer theory, the Gibbs energy fluxes Internal energy transfer theory is motivated from the thermo-
are described as a function of chemical potential, time, and dynamic point of view in which internal energy transfer depends
displacement simultaneously under a postulate that chemical po- on intensive state variables as well as extensive state variables.
tential, time, and displacement are independent and orthogonal Internal energy transfer in a quasi-equilibrium (quasi-static) pro-
variables in extended phase spaces. This is the first rigorous cess is conventionally described only by extensive state variables,
microscopic kinetic theory for internal convective chemical energy but internal energy in a non-equilibrium process can be stated by
transfer. including intensive state variables. Here, the dependence of
External convective energy transfer is formulated in addition to intensive state variables for internal energy transfer is discussed
internal convective energy transfer. Moreover, the thermodynamic [30,31,33].
behavior of the equilibrium chemical process is clarified through Euler's equation of thermodynamics for the internal energy is
the theory. A connection between a rate equation and a reaction
quotient is also proved through the chemical energy transfer theory U (T, S, P, V, m, N) ¼ TS  PV þ mN.
since they are dependent on both concentration and temperature.
Fig. 1 sketches the hierarchy for energy transfer which consists From Euler's equation, we have the first law of thermodynamics:
of heat, work, and chemical energy transfer [30e36]. Each energy
transfer possesses three modes of conduction (or diffusion), con- dU ¼ dQ  dW þ dG.
vection, and radiation in addition to equilibrium. Aside from radi-
ation, this paper concentrates on internal convection, conduction, Rewriting the first law, we obtain
internal equilibrium, and convection of chemical energy transfer to
explore chemical reactions. Moreover, the statistical thermody- dU (T, S, P, V, m, N) ¼ (TdS  PdV þ mdN) þ (SdT  VdP þ Ndm) (2)
namic theory of electrochemical reactions is reviewed as a branch
of the chemical energy transfer. where
The objective of this paper is hence to establish a chemical en-
ergy transfer theory for chemical reactions and to apply the dQ (T, S) ¼ TdS þ SdT,

Please cite this article in press as: Roh H-S, Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and
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 H.-S. Roh / Energy xxx (2015) 1e21 3

dW (P, V) ¼ PdV þ VdP, Irreversible non-equilibrium processes take place if T > Ta, P > Pa,
and m > ma while reversible equilibrium processes occur if T < Ta,
dG (m, N) ¼ mdN þ Ndm. P < Pa, and m < ma. Table 1 summarizes non-equilibrium, quasi-
equilibrium, and equilibrium processes.
For a quasi-equilibrium process, the fundamental equation of Irreversible non-equilibrium processes take place if T > Ta,
thermodynamics is given by P > Pa, and m > ma while reversible equilibrium processes occur if
T < Ta, P < Pa, and m < ma:
dU (S, V, N) ¼ TdS  PdV þ mdN,
Internal energy transfer, dU (T, S, P, V, m, N) ¼
where the GibbseDuhem equation is observed: (TdS  PdV þ mdN) þ (SdT  VdP þ Ndm),

SdT  VdP þ Ndm ¼ 0. Heat transfer, dQ (S, T) ¼ TdS þ SdT,

On the other hand, for a non-equilibrium or equilibrium process, Work transfer, dW (V, P) ¼ PdV þ VdP,
we have
Chemical energy transfer, dG (N, m) ¼ mdN þ Ndm,
dU (S, V, N) < TdS  PdV þ mdN.
Irreversible quasi-equilibrium processes take place if T > Ta,
Combining non-equilibrium, quasi-equilibrium, and equilibrium P > Pa, or m > ma while reversible quasi-equilibrium processes occur
processes, we can rewrite if T < Ta, P < Pa, or m < ma:

dU (S, V, N)  TdS  PdV þ mdN, (3) Internal energy process, dU (T, P, m) ¼ SdT  VdP þ Ndm ¼ 0,

which is the fundamental thermodynamic relation. Isothermal process, dQ (S) ¼ TdS if dT ¼ 0,

Comparing Eq. (2) with Eq. (3), we can analyze that
Isobaric process, dW (V) ¼ PdV if dP ¼ 0,
SdT  VdP þ Ndm  0. (4)
Constant chemical potential process, dG (N) ¼ mdN if dm ¼ 0.
From the above equation, we have the conditions of distinct ther-
modynamic processes: Irreversible quasi-equilibrium processes take place if T > Ta,
For a quasi-equilibrium process, it reduces to the GibbseDuhem P > Pa, or m > ma while reversible quasi-equilibrium processes occur
equation if T < Ta, P < Pa, or m < ma:

SdT  VdP þ Ndm ¼ 0. Internal energy process, dU (S, V, N) ¼ TdS  PdV þ mdN ¼ 0,

For a non-equilibrium or equilibrium process, it holds the
inequality condition
SdT  VdP þ Ndm > 0.
Distinction between non-equilibrium and equilibrium depends on
whether temperature, pressure, and chemical potential are larger
than their corresponding activation temperature, activation pres-
sure, and activation chemical potential.
In summary, we analyze that there are two contributions in
internal energy transfer in Eq. (2). The first contribution originates
from external variable changes, and the second contribution comes
from the internal variable changes. The GibbseDuhem relation
holds only for the quasi-equilibrium process.
Based on Eq. (2), we can specifically classify non-equilibrium,
quasi-equilibrium, and equilibrium processes. We utilize the defi-
nitions of the thermodynamic potentials:
Gibbs free energy, G ¼ U  TS þ PV ¼ mN,
Heat potential, Q ¼ U þ PV  mN ¼ TS,
Grand potential, W ¼ U  TS  mN ¼ PV.
We also employ the activation points of intensive variables from
equilibrium to non-equilibrium:
Activation temperature, Ta,
Activation pressure, Pa,
Activation chemical potential, ma,
Isentropic process, dQ (T) ¼ SdT if dS ¼ 0,
Isochoric process, dW (P) ¼ VdP if dV ¼ 0,
Constant particle number process, dG (m) ¼ Ndm if dN ¼ 0.
In general, internal energy transfer indicated by Eq. (2) contains
contributions from temperature change, pressure change, and
chemical potential change due to the internal degrees of freedom in
addition to the external variable changes. In addition, we adopt the
fact that internal energy transfer depends on space and time due to
the external degrees of freedom.
2.2. Internal energy transfer theory
We utilize a postulate that the internal energy flux (or internal
energy intensity) can be described as a function of temperature,
pressure, chemical potential, time, and space:
u ¼ u (T, P, m, t, r).
It is assumed that the five variables are independent and orthog-
onal. Furthermore, the expression of the internal energy flux can be
written as a product of temperature, pressure, chemical potential,
time, and space dependent terms:
u ¼ q(T)w(P)g(m)B(t)A(r).
The internal energy flux in thermodynamics under the postulate
is described by a partial differential equation:

Please cite this article in press as: Roh H-S, Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and
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4 H.-S. Roh / Energy xxx (2015) 1e21

Table 1
Non-equilibrium, quasi-equilibrium, and equilibrium processes of energy transfer.

Energy transfer Irreversible or reversible quasi-equilibrium Non-equilibrium or equilibrium

Chemical energy dG (m) ¼ Ndm if dN ¼ 0. dG (N) ¼ mdN if dm ¼ 0 dG (N, m) ¼ mdN þ Ndm

Thermal energy dQ (T) ¼ SdT if dS ¼ 0 dQ (S) ¼ TdS if dT ¼ 0 dQ (S, T) ¼ TdS þ SdT
(heat)
Mechanical energy dW (P) ¼ VdP if dV ¼ 0, dW (V) ¼ PdV if dP ¼ 0 dW (V, P) ¼ PdV þ VdP
(work)
Internal energy dU (S, V, N) ¼ TdS  PdV þ mdN ¼ 0 dU (T, P, m) ¼ SdT  VdP þ Ndm ¼ 0 dU (T, S, P, V, m, N) ¼ (TdS  PdV þ mdN) þ (SdT  VdP þ Ndm)

lV$u þ t Du/Dt ¼ 0 (5) vg/vm þ (n/kBT0) g(m) ¼ 0, (11)

where u ¼ un is the total energy flux vector (or the power density vB/vt þ (b /t) B(t) ¼ 0, (12)
vector) with the unit vector n. The internal energy flux u is defined
by internal energy per unit area and unit time. t is the total reaction V$А þ (k/l) А(r) ¼ 0. (13)
time which is defined by the mean reaction time t0 multiplied by
the particle number of the system, and l is the total mean free path Eq. (9) represents the heat transfer equation, and Eq. (10) stands for
which is defined by the mean free path l0 multiplied by the particle the work transfer equation. Eq. (11) shows the chemical energy
number of the system. transfer equation and leads to the Nernst equation. Eq. (12) and (13)
D/Dt represents the thermodynamic convective derivative: reflect the temporal and spatial equations for energy transfer,
respectively.
D/Dt ¼ v/vt þ vT$VΤ The five constants a, z, n, b, and k in the separation of variables
¼ v/vt  [T0 v/vΤ þ (kBT0/ v0) v/vP þ kBT0 v/vm]/t (6) are introduced:

where Τ is the temperature, P is the pressure, and m is the chemical a: thermal particle number constant,
potential. v0 is the equilibrium volume V0 per particle number, T0 is z: mechanical particle number constant,
the equilibrium temperature, and kB is the Boltzmann constant. In n: chemical particle number constant,
Eq. (6), we introduce the thermodynamic velocity vector b: temporal particle number constant,
k: spatial particle number constant.
vT ¼ l/t (i þ j þ k)
The particle number constants in the above are constrained by:
and the thermodynamic derivative vector In nonrelativistic case,

VΤ ¼ (i T0v/vΤ þ j P0v/vP þ k m0v/vm)/l. a þ z þ n ¼ d,

The intrinsic intensive property dimensions of temperature, pres- d þ k  b ¼ 0.

sure, and chemical potential play the roles of momentum di-
mensions in a material space and their corresponding extensive
dimensions of entropy, volume, and particle number do the roles of
space dimensions or vice versa. They behave as independent di-
mensions in a material space like the conventional space and mo-
mentum dimensions.
Eq. (5) can be fully expressed as
lV$u  [T0 vu/vΤ þ (kBT0/v0) vu/vP þ kBT0 vu/vm] þ tvu/vt ¼ 0. (7)
The first term in the bracket of Eq. (7) represents the heat transfer,
the second term the work transfer, and the third term the chemical
energy transfer of the system in a micro-canonical ensemble. Eq. (7)
may become the thermodynamic extension of the Liouville equa-
tion since the thermodynamic intensive variables in Eq. (7) are
included as phase spaces and the internal energy flux in Eq. (7) is
proportional to the phase space distribution in the Liouville equa-
tion [38,39].
We deal with the internal convective and external diffusion
effects in Eq. (7). Using the method of separation of variables for the
internal energy flux
u (Τ, P, m, t, r) ¼ q(Τ)w(P)g(m)B(t)A(r), (8)
we derive five differential equations from (7):
vq/vΤ þ (a/T0) q(Τ) ¼ 0, (9)
In relativistic case,
a2 þ z2 þ n2 ¼ d2,
d2 þ k2  b2 ¼ 0.
The thermal particle number constant in Eq. (9) is connected to
the entropy change by a ¼ ln U ¼ S/kB where U is the number of
microstates in the microcanonical ensembles. The equilibrium
volume per particle number in Eq. (10) is related to k by v0 ¼ V0/k. n
in Eq. (11) represents the particle number change in specific par-
ticle species. kr ¼ b/t ¼ 1/t0 in Eq. (12) stands for the rate constant
in internal energy transfer and is the inverse of the mean reaction
time t0. k ¼ (b2  d2)1/2 ¼ l/l0 in Eq. (13) is connected to the re-
action cross section sc ¼ V/kl0 ¼ v0/l0.
As for the solutions of internal convection and diffusion energy
fluxes (uu and ud) in the non-equilibrium process of nonzero T, P, m,
t, and r, we find the following integrated solutions from (9)e(13),
respectively:
q(ΤS) ¼ q0 exp (aΤS/T0), (14)
w(PV) ¼ w0 exp (zv0PV/kBT0), (15)
g(mN) ¼ g0 exp (nmN/kBT0), (16)

vw/vP þ (zv0 /kBT0) w(P) ¼ 0, (10) B(tB) ¼ B0 exp (btB/t), (17)

Please cite this article in press as: Roh H-S, Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and
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 H.-S. Roh / Energy xxx (2015) 1e21
А(rB) ¼ A0 exp (k$rB/l), (18)
where k ¼ kn ¼ (b2  d2)1/2n and n is the unit vector along the diffusion
direction of the energy flux. Eq. (14)e(16) reflect the Arrhenius type
equations. Eq. (15) represents the equation of state, Eq. (17) denotes the
reaction frequency, and Eq. (18) indicates the steric factor.
To apply the boundary and initial conditions to Eq. (14)e(18), we
utilize the excess temperature, pressure, chemical potential, time,
and displacement measured from their relative equilibriums,
respectively:
ΤS ¼ jT  T0j,
PV ¼ jP e P0j,
mN ¼ jm  m0j,
tB ¼ jt  t0j,
rB ¼ jr  r0jn.
At large TS, PV, mN, rB, or tB, the corresponding energy flux amplitude
approaches to zero.
The process with nonzero a, z, and n represents the coupled
transfer with heat, work, and chemical energy transfer in a system,
and the relevant thermodynamic potential change is the internal
energy change DU since the microcanonical ensemble system does
not interact with environment. The system process takes place
under the constant entropy, particle number, and volume. The in-
ternal energy flux takes the form
0
u (ΤS, PV, mN, tB, rB) ¼ u0 exp [(akBΤS þ zv0PV þ nmN)/kBT0] exp (btB/t) exp (k$rB/l)
0
¼ u0 exp [(DQS  DWV þ DGN)/kBT0] exp (btB/t) exp (k$rB/l)
00
¼ u exp (DUB/kBT0) exp (btB/t) exp (k$rB/l)
0
where u0 ¼ q0w0g0B0A0.
The heat reaction quotient Zq ¼ exp(DQS/kBT0) for a heat
ensemble, the work reaction quotient Zw ¼ exp(DWV/kBT0) for a
grand canonical ensemble, and the Gibbs reaction quotient
Zg ¼ exp(DGN/kBT0) for a Gibbs ensemble. Hence, we analyze that
DQS ¼ (DQ  DQ0) ¼ akBΤS ¼ akBjT  T0j,
DWV ¼ (DW  DW0) ¼ zVPV ¼ zv0jP e P0j,
DGN ¼ (DG  DG0) ¼ nmN ¼ njm  m0j,
DUB ¼ (DU  DU0) ¼ DQS  DWV þ DGN.
3. Chemical energy transfer theory for chemical reactions
We are interested in chemical energy transfer which is regarded
as a special case of the internal energy transfer theory22 with the
designated particle number constants (nonzero n, b, and k;
a ¼ z ¼ 0). A chemical reaction is a process that leads to the
transformation of one set of chemical substances to another. A total
system containing reactants and products is chemically isolated
from its surroundings and is in chemical non-equilibrium while the
two phases of reactants and products are in thermal and me-
chanical isolation. For the system in chemical non-equilibrium, the
physical mechanisms of energy transfer can be described by
physical parameters in local thermodynamic equilibrium.
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5
The statistical thermodynamic theory for electrochemical re-
actions [31,32] is generalized for a statistical thermodynamic theory
for chemical reactions. Chemical reactions can be either spontaneous
or non-spontaneous. The Gibbs potential in chemical energy transfer
is defined by G ¼ SmiNi and the Gibbs energy transfer per area per unit
time between reactants and products can be defined by g ¼ (Smin0i -
Smkn0k) where n0 is the particle density per area per unit time.
A chemical reaction involves a dissociation of a molecule into
fragments or a chemical synthesis from two molecules to a merger:
AB ———> B þ C,
B þ C ———> AB.
More general chemical reactions take the form
oO þ pP ———> rR þ sS.
The Gibbs energy change in a chemical reaction DG is defined by
DG ¼ G(products)  G (reactants) ¼ Gp  Gr. (20)
We adopt a postulate that the Gibbs energy flux can be
described as a function of chemical potential, time, and space:
g ¼ g (m, t, r).
Furthermore, the expression of the Gibbs energy flux can be written
as a product of chemical potential, time, and space dependent
terms:
(19)
g ¼ g(m)B(t)A(r).
To describe chemical reactions, Eq. (7) can be expressed as
l V$g  kBT0 vg/vm þ t vg/vt ¼ 0 (21)
where g ¼ gn is the Gibbs energy flux vector with the unit vector n.
The second term represents the internal convective Gibbs energy
transfer in the chemically isolated system under constant temper-
ature and constant pressure.
A hypothesis dealing with convective chemical reactions is that
chemical energy transfer is proportional to chemical energy
change: g f Dm. A restriction is that the chemical energy transfer
satisfies the Arrhenius type equation. The chemical potential plays
the role of an independent dimension such as space or time.
Eq. (21) is the extension of energy density conservation:
l V$g þ t vg/vt ¼ 0 (22)
where va ¼ l/t is the average particle speed and g ¼ gd þ gv is the
Gibbs energy flux of diffusion and convection. Eq. (22) is the
transform of the continuity equation
V$g þ emvn0/vt ¼ 0
where n0 is the particle number density, em is the Gibbs energy
change per particle, and emn0 ¼ g/va is the Gibbs energy change per
unit volume.
6 H.-S. Roh / Energy xxx (2015) 1e21

The external Gibbs energy flux in the first term of Eq. (21) is
comprised of the convection energy flux gv and the diffusion energy
flux gd:

g ¼ gd þ gv.

The internal Gibbs energy flux in the second term of Eq. (21) is
made of the internal convection energy flux gm and the internal
equilibrium energy flux g0:

g ¼ gm þ g0.
Fig. 3. Hierarchy in chemical reactions.
Fig. 2 presents the chemical energy transfer theory dealing with
the four regions of non-equilibrium, irreversible quasi-equilibrium,
where n0 is the particle number density and em is the chemical
reversible equilibrium and equilibrium. The theory offers governing
energy per particle.
equations for the internal equilibrium, internal convection, external
We deal with the diffusion and internal convective effects.
convection, and conduction mechanisms. Fig. 3 exhibits relation-
When we use the method of separation of variables for the Gibbs
ships among these processes. Non-equilibrium reactions contain
energy flux
internal convection processes, and equilibrium reactions represent
internal equilibrium processes. Quasi-equilibrium reactions of
gm(m, t, r) ¼ g(m) B(t) A(r),
external convection and diffusion include migration and concen-
tration diffusion processes. Governing equations and solutions in
we derive the following three differential equations from Eq. (23):
the four regions are described in the following sections.
Relationships among subjects in the chemical energy transfer
vg/vm þ (n/kBT0) g(m) ¼ 0, (24)
theory of chemical reactions are shown in Fig. 4. The chemical energy
transfer theory renders the reaction quotient, and thermodynamics
vB/vt þ (b /t) B(t) ¼ 0, (25)
defines the reaction quotient. In chemical equilibrium, the equilib-
rium constant is defined and is estimated by statistical mechanics.
V$A þ (k/l) A(r) ¼ 0. (26)
Conventional transport phenomena near equilibrium are connected
to the equations of diffusion and migration. The rate equation known
Eq. (24) denotes the chemical energy transfer. Eqs. (25) and (26)
as the kinetics of chemical reactions is derived as a special case of the
represent the temporal and spatial equations for chemical energy
chemical energy transfer theory. Thermodynamics, statistical me-
transfer, respectively.
chanics, and kinetics viewpoints depend on energy, probability, and
The three constants n, b, and k in the separation of variables are
rate considerations, respectively.
introduced, and their constraint is expressed as:
In nonrelativistic case,
4. Chemical energy transfer for non-equilibrium chemical
reactions n þ k  b ¼ 0.

4.1. Non-equilibrium chemical reactions In relativistic case,

The governing equation for non-equilibrium chemical reactions n2 þ k2  b2 ¼ 0.

can be expressed as
The relativistic constraint is applied to classify different processes
l V$gm  kBT0 vgm/vm þ t vgm/vt ¼ 0. (23) even though nonrelativistic governing equations are addressed.
Τhe separation constants indicate.
The above equation is the extension of the continuity equation for
diffusion: n: chemical particle number constant,
b: temporal particle number constant,
V$gd þ em vn0/vt ¼ 0 k: spatial particle number constant.

Fig. 2. Four chemical energy transfer regions of non-equilibrium, irreversible quasi- Fig. 4. Relationships among subjects in the chemical energy transfer theory of
equilibrium, reversible quasi-equilibrium and equilibrium. chemical reactions.

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 H.-S. Roh / Energy xxx (2015) 1e21
Eq. (25) represents the rate equation in chemical reactions.
kr ¼ b/t ¼ 1/t0 in Eq. (25) stands for the rate constant in chemical
reactions and is the inverse of the mean reaction time t0.
k ¼ (b2  n2)1/2 ¼ l/l0 in Eq. (26) is connected to the reaction cross
section sc ¼ V/kl0, and n0 ¼ k/V is the particle number per unit
volume. We can make use of the particle number constants to
classify chemical energy transfer mechanisms.
With respect to the internal convection and conduction chem-
ical energy flux (gm and gd) in the non-equilibrium process of
nonzero m, t, and r, we obtain the three integrated solutions from
(24), (25), and (26), respectively:
g(mN) ¼ g0 exp (nmN/kBT0), (27)
B(tB) ¼ B0 exp (btB/t), (28)
A(rB) ¼ A0 exp (k$rB/l), (29)
2 2 1/2
where k ¼ kn ¼ (b  n ) n and n is the unit vector in the
diffusion direction of the Gibbs energy flux.
Eqs. (27)e(29) satisfy the initial and boundary conditions. The
chemical potential, time, and displacement variables are repre-
sented as the excess quantities, respectively:
mN ¼ jm  m0j,
tB ¼ t  t0,
rB ¼ jr  r0jn. (30)
At large mN, rB, or tB, the corresponding chemical energy flux
amplitude converges to zero.
The chemical energy density is thus of the final form:
0
gm(mN, tB, rB) ¼ g0 exp (nmN/kBT0) exp (btB/t) exp (k$rB/l) (31)
00 00
where g ¼ g0 B0 A0. The normalization condition for g may yield
00
g ¼ n0 (ek þ Pv0) va ¼ (k/V)emva
where va ¼ (8kBT0/m0p)1/2 is the mean speed in thermal
equilibrium.
Eq. (27) can be utilized to understand the Gibbs energy flux as a
function of chemical potential. It also has a form of the Arrhenius
type equation and a connection to the Gibbs energy change.
Therefore, the relationships among thermodynamics, statistical
mechanics, and chemical reactions can be explored. In terms of Eq.
(27), the relative chemical energy transfer, actual chemical energy
transfer, chemical energy reaction quotient, and chemical potential
are respectively defined by
DGN ¼ DG  DG0 ¼ nmN ¼ njm  m0j,
DG ¼ DG0 þ kBT0 ln Zg,
Zg ¼ exp (DGN/kBT0),
m ¼ m0  (kBT0/n) ln Zg. (32)
These equations may be useful to explore the chemical energy
transfer. In chemical reactions,
K ¼ exp (DGN/RT0)
where K is the reaction quotient and R is the universal gas constant.
Therefore, a relation between the Gibbs reaction quotient and the
reaction quotient is obtained:
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7
Zg ¼ KNa
where Na is Avogadro's number.
Once the process surpasses the activation chemical potential,
the zero or nonzero n process takes place. The process of n ¼ 0
represents the chemical energy transfer process due to the diffu-
sion mechanism after the process reaches the activation chemical
potential. The zero n process is of irreversible diffusion while the
nonzero n process is of irreversible internal convection.
Eq. (28) provides the time rate of a chemical reaction, and the
reaction equation is given by Eq. (25). The temporal particle num-
ber constant b gives the information of process speed. From Eq.
(28), the behavior of time is obtained:
t ¼ t0  (t /b) ln M ¼ t0  t0 ln M
where M ¼ B/B0 ¼ gt/g0t with the exchange chemical energy flux g0t
is the temporal chemical (Gibbs) energy partition function. Since
the conventional rate constant kr is related to the temporal particle
number constant by kr ¼ b/t ¼ 1/t0, Eq. (28) is analogous to the rate
law of the first order or the pseudo-first order chemical reaction
under the assumption that the quantity B is proportional to the
concentration:
vB/vt þ kr B(t) ¼ 0.
Eq. (29) leads to the spatial dependence of the convection en-
ergy process. The spatial particle number constant k affords the
information of the reaction cross section, the diffusion speed, and
the process stability in spaces. The relation between the reaction
cross section sc and the spatial particle number constant k is
sc ¼ V/kl0:
sc ¼ 1/n0l0.
From Eq. (29), the spatial coordinate is given by
r ¼ r0  n(l/k) ln L ¼ (r0  l0 ln L)n
where L ¼ A/A0 ¼ gr/g0r with the exchange chemical energy flux g0r
is the spatial chemical energy (Gibbs) reaction quotient.
4.2. Special cases of chemical reactions
In the following, we address special cases of the chemical energy
transfer theory (21): non-equilibrium, irreversible quasi-
equilibrium, reversible quasi-equilibrium, and equilibrium energy
transfer. The particle number constants of n, b, and k along with mN
and m0 especially play the major roles to describe the distinctive
processes. Table 2 classifies thermodynamic, spatial, and temporal
energy transfer mechanisms in equilibrium, reversible quasi-
equilibrium, irreversible quasi-equilibrium, and non-equilibrium.
Spontaneity conditions for chemical energy transfer processes are
closely connected to the values of the particle number constants as
shown in Table 3. Table 4 displays the processes of reversible and
irreversible quasi-equilibrium chemical energy transfer mecha-
nisms. Table 5 summaries the thermodynamics laws of reversible
and irreversible chemical energy transfer mechanisms.
In non-equilibrium chemical reactions for a nonzero n, the Gibbs
energy change is not zero: nonzero DGN. Two possible processes are
analyzed:
Unsteady and uniform chemical reactions with n2  b2 ¼ 0
(nonzero n, mN and b; k ¼ 0).
Non-uniform and steady chemical reactions with n2 þ k2 ¼ 0
(nonzero n, mN, and k; b ¼ 0).
8 H.-S. Roh / Energy xxx (2015) 1e21

Table 2
Thermodynamic, spatial, and temporal energy transfer mechanisms.

Energy transfer Thermodynamics Space Time

Chemical energy Equilibrium m ¼ 0 for njm  m0j r ¼ 0 for k$jr  r0jn t ¼ 0 for bjt  t0j
Reversible quasi-equilibrium n ¼ 0, m0 s 0 k ¼ 0, r0 s 0 b ¼ 0, t0 s 0
m0 ¼ 0, n s 0 r0 ¼ 0, k s 0 t0 ¼ 0, b s 0
Irreversible quasi-equilibrium n ¼ 0, mN s 0 k ¼ 0, rB s 0 b ¼ 0, tB s 0
mN ¼ 0, n s 0 rB ¼ 0, k s 0 tB ¼ 0, b s 0
Non-equilibrium nmN ¼ njm  m0j s 0 k$rB ¼ k$jr  r0jn s 0 btB ¼ bjt  t0j s 0
Internal energy Equilibrium T ¼ P ¼ m ¼ 0 for akBΤSþzv0PV þ nmN r ¼ 0 for k$jr  r0jn t ¼ 0 for bjt  t0j
Reversible quasi-equilibrium a ¼ z ¼ n ¼ 0 nonzero Τ0,P0,m0 k ¼ 0, r0 s 0 b ¼ 0, t0 s 0
Τ0 ¼ P0 ¼ m0 ¼ 0 r0 ¼ 0, k s 0 t0 ¼ 0, b s 0
Irreversible Quasi-equilibrium a ¼ z ¼ n ¼ 0 nonzero ΤS, PV, mN k ¼ 0, rB s 0 b ¼ 0, tB s 0
ΤS ¼ PV ¼ mN ¼ 0 rB ¼ 0, k s 0 tB ¼ 0, b s 0
Non-equilibrium akBΤS þ zv0PV þ nmN s 0 k$rB ¼ k$jr  r0jn s 0 btB ¼ bjt  t0j s 0

Table 3
Spontaneity conditions for chemical energy transfer mechanisms.

Energy transfer Thermodynamics Space Time

Chemical energy Spontaneous n>0 k >0 b>0

Equilibrium n¼0 k ¼0 b¼0
Non-spontaneous n<0 k <0 b<0
Internal energy Spontaneous d>0 k >0 b>0
Equilibrium a¼z¼n¼d¼0 k ¼0 b¼0
Non-spontaneous d<0 k <0 b<0

The governing equation for steady and uniform chemical energy where m is the chemical potential and C is the particle number
transfer leads to density. In non-equilibrium, the differential Eq. (35) leads to two
equations for the intensive and the extensive variable under the
kBT0 vgm/vm  t vgm/vt ¼ 0. (33) assumption that m and C are orthogonal and independent:

The chemical energy density takes the integrated solution: l V$C  kBT0 vC/vm þ t vC/vt ¼ 0,
0
gm(mN, tB) ¼ g0 exp (nmN/kBT0) exp (btB/t) l V$m  kBT0 þ t vm/vt ¼ 0.
00
where g ¼ g0B0 and b2 ¼ n2. Rewriting the above equations, we find
Non-uniform and steady chemical energy transfer is given by
the partial differential equation: V$jdd  (kBT0/t)vC/vm þ vC/vt ¼ 0,

l V$gm  kBT0 vgm/vm ¼ 0. (34) V$jdm  (kBT0/t) þ vm/vt ¼ 0,

The chemical energy density is thus of the final form: where Fick's first law jdd ¼ Cva ¼ D0VC and the migration current
density jdm ¼ mva ¼ DmVm are utilized under the assumption of
0
gm(mN, rB) ¼ g0 exp (nmN/kBT0) exp (k$rB/l) constant temperature and constant pressure. The first is the con-
centration diffusion equation for an isotropic process, and the
0
where g0 ¼ g0A0 and k2 ¼ n2. second is the migration equation for an isotropic process:

5. Chemical energy transfer for irreversible quasi- D0V2C  vC/vt ¼ (kBT0/t)vC/vm, (36)
equilibrium chemical reactions
DmV2m  vm/vt ¼ kBT0/t, (37)
The internal source Ci in Eq. (1) can be identified from Eq. (23).
Eq. (23) can be written as where D0 ¼ val0/3 is the concentration diffusion coefficient and
Dm ¼ val0/3 ¼ l20/3t0 is the migration coefficient. Ci ¼ (kBT0/t) vC/vm
m[l V$C  kBT0 vC/vm þ t vC/vt] þ C[l V$m  kBT0 þ t vm/vt] is obtained by comparing Eq. (1) with Eq. (36). This means chemical
¼0 (35) internal convection becomes the source in the concentration

Table 4
Reversible and irreversible quasi-equilibrium chemical energy transfer mechanisms.

Energy transfer Process Variable Reversible quasi-equilibrium Irreversible quasi-equilibrium

(convection) (diffusion)

Chemical energy Chemical potential n¼0 n¼0

(Migration) m0 s 0 mN s 0
Particle number ns0 ns0
(Diffusion) m0 ¼ 0 mN ¼ 0

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 H.-S. Roh / Energy xxx (2015) 1e21 9

Table 5
Thermodynamics laws of reversible and irreversible chemical energy transfer mechanisms.

Energy transfer Process Variable Reversible equilibrium Irreversible non-equilibrium

and quasi-equilibrium and quasi-equilibrium

Chemical energy Chemical potential Conservation Decrease

Particle number Conservation Increase

diffusion equation. The condition for the particle number constants vg0/vm  (n/kBT0) g0 (m) ¼ 0, (42)
in Eq. (36) leads to b2 ¼ n2 þ k2.
During quasi-equilibrium chemical reactions, two irreversible vB0/vt  (b/t) B0 (t) ¼ 0, (43)
processes are possible:
Migration with b2 ¼ n2 þ k2 (nonzero b and k; n ¼ 0), V$A0  k A0 (r) ¼ 0. (44)
Concentration diffusion with b2 ¼ k2 (nonzero b and k; mN ¼ 0).
Quasi-equilibrium transport theories for conduction chemical The three constants n, b, and k in the separation of variables are
reactions are considered as special cases of general chemical re- linked to
actions (1). Migration and diffusion equations are derived. The
governing equation for diffusion and migration is found to be n2 þ k2  b2 ¼ 0.

l V$gd þ t vgd/vt ¼ 0. (38) Eqs. (42)e(44) then yield the following integrated solutions
respectively:
The zero n process in Eq. (37) represents the chemical energy
migration at constant particle number. The migration equation g0 (m0) ¼ g0 exp (nm0/kBT0), (45)
becomes
B0 (t0) ¼ B0 exp (bt0/t), (46)
DmV2m  vm/vt ¼ 0. (39)
A0 (r0) ¼ A0 exp (k$r0/l), (47)
The requirement for the particle number constants is b2 ¼ k2.
The process of mN ¼ jmm0j ¼ 0 in Eq. (36) is the particle diffusion where k ¼ kn ¼ (b2  n2)1/2n and n is the unit vector in the
at constant chemical potential. Eq. (36) leads to Fick's second law: diffusion direction of the Gibbs energy flux.
Eqs. (45)e(47) satisfy the initial and boundary conditions. Note
D0V2C  vC/vt ¼ 0. (40) that Eqs. (27)e(29) lead to Eqs. (45)e(47) at T ¼ t ¼ r ¼ 0,
respectively. The chemical energy density is thus of the final form:
The constraint for the particle number constants is b2 ¼ k2.
0
g0(m0, t0, r0) ¼ g0 exp (nm0/kBT0) exp (bt0/t) exp (k$r0/l) (48)
6. Chemical energy transfer for equilibrium chemical
reactions where g0’ ¼ g0 B0 A0.
The activation chemical potential ma, the activation time ta, and
Chemical energy transfer for equilibrium is the reversible pro- the activation displacement ra are used in the above:
cess of (nonzero n, b, and k; m ¼ t ¼ r ¼ 0). The equilibrium process p
takes place at a nonzero m0 ¼ jmp0  mr0j while the chemical potentials ma ¼ jm0  mr0jmax ¼ jm  m0jmax,
between reactants and products are the same, mp ¼ mr; m ¼ 0 in (30). p
Note that m0 is a variable depending on the chemical potential ta ¼ jt0  tr0jmax ¼ jt  t0jmax,
difference between mp0 and mr0 while m0 is the equilibrium chemical p
potential. Similarly, the spatial and temporal equilibriums are ra ¼ jr0  rr0jmax ¼ jr  r0jmax. (49)
attained at t ¼ r ¼ 0 in (30), but t0 and r0 are nonzero variables.
The equilibrium chemical potential, time, and displacement The integrated solutions of (45)e(47) satisfy g0(m0 ¼ 0) ¼ g0,
variables are parameterized as the excess quantities, respectively: B0(t0 ¼ 0) ¼ B0, and A0(r0 ¼ 0) ¼ A0 at the boundary and initial
conditions of m0 ¼ 0, t0 ¼ 0, and r0 ¼ 0, which stand for chemical,
p temporal, and spatial equilibriums. Moreover, they satisfy
m0 ¼ jm0  mr0j ¼ jm  m0j,
g0(m0 ¼ ma) ¼ g1, B0(t0 ¼ ta) ¼ B1, and A0(r0 ¼ ra) ¼ A1 at the limiting
p
t0 ¼ t0  tr0 ¼ t  t0, conditions of m0 ¼ ma, t0 ¼ ta, and r0 ¼ ra. A variable with the
subscript a denotes the threshold value, and an amplitude variable
p with the superscript 1 indicates its limiting value. Using the initial
r0 ¼ jr0  rr0jn ¼ jr  r0jn.
and limiting conditions, we can evaluate the particle number
Under the parameterization, the governing equation for equi- constants:
librium chemical reactions becomes
n ¼ (kBT0/ma) ln (g1/g0),
l V$g0  kBT0 vg0/vm þ t vg0/vt ¼ 0. (41)
b ¼ (t/ta) ln (B1/B0),
When the method of separation of variables for the Gibbs energy
flux k ¼ (l/ra) ln (A1/A0).

g0(m, t, r) ¼ g0(m) B0(t) A0(r) The Gibbs equilibrium constant has the relation

is used, three differential equations are obtained from (41): Z0g ¼ exp (DG0/kBT0),

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10 H.-S. Roh / Energy xxx (2015) 1e21
and the equilibrium constant K0 takes the form
K0 ¼ exp (DG0/RT0)
¼ exp (nm0/RT0)
¼ exp (njm  m0j/RT0).
Rewriting the above equation, we get the chemical potential during
equilibrium chemical reactions:
m ¼ m0 þ (RT0/n) ln K0. (50)
7. Chemical energy transfer for reversible quasi-equilibrium
chemical reactions
Chemical energy transfer for reversible quasi-equilibrium is the
convection process of (nonzero b and k; n ¼ t ¼ r ¼ 0 or
mN ¼ t ¼ r ¼ 0). The spatial and temporal equilibriums are attained
at t ¼ r ¼ 0 in (30). The governing equation becomes
lV$gv þ t vgv/vt ¼ 0. (51)
The particle number constants have a relation:
k2  b2 ¼ 0.
The equilibrium Gibbs energy flux thus has the final form:
0
gv (t, r) ¼ g0 exp (bt0/t) exp (k$r0/l)
0
where g0 ¼ B0 A0.
Eq. (51) leads to the chemical potential conservation (nonzero b
and k; mN ¼ t ¼ r ¼ 0) and particle number conservation (nonzero b
and k; n ¼ t ¼ r ¼ 0):
vm/vt þ V$(mva) ¼ 0,
vC/vt þ V$(Cva) ¼ 0. (52)
In the presence of convection and diffusion process, the con-
centration diffusion-convection equation and the migration-
convection equation are given by
V2C  (1/D0) vC/vt  (1/D0) va$VC ¼ 0,
V2m  (1/Dm) vm/vt  (1/Dm) va$Vm ¼ 0. (53)
8. Statistical thermodynamic theory for electrochemical
reactions
An electrochemical reaction is a branch of a chemical reaction,
as emphasized in Fig. 1. The connection between chemical and
electrochemical reactions is considered here. The statistical ther-
modynamic theory to describe electrochemical reactions has been
proposed [31,32]. A total system is in chemical non-equilibrium
while it is in thermal and mechanical equilibrium. The current
density in thermodynamic non-equilibrium in continuous media is
characterized as the intensive variable, electric potential.
To make sure that an electrochemical reaction is one of chemical
reactions, following relationships among thermodynamic proper-
ties are described. The relation between the current density j and
the Gibbs energy transfer per unit area and unit time is given by
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DG/tA ¼ zeFE/tA ¼ jE with the electric potential E. The relation
between the Gibbs potential and the chemical potential is DG/
N ¼ Dm where the other relations are Dm ¼ zeFE and N ¼ jV/zeFv
with the volume V and the velocity v. In the following, the current
density as a function of electric potential is demonstrated instead of
the Gibbs energy flux as a function of chemical potential.
The partial differential equation for chemical reaction (23) leads
to a partial differential equation:
lV$gE  (RT0/F) vgE/vЕ þ t dgE/dt ¼ 0 (54)
where gE ¼ jEE ¼ gn is the Gibbs energy flux vector with the unit
vector n. The Gibbs energy flux is defined as the Gibbs energy
change per unit area and unit time.
Eq. (54) reduces to
E[l V$jE  (RT0/F) vjE/vЕ þ t djE/dt] þ j[l V$E  RT0/F þ t dE/dt] ¼ 0.
Under the assumption that the current density and the electric
potential are orthogonal and independent, we obtain two equa-
tions from the above equation:
l V$jE  (RT0/F) vjE/vЕ þ t djE/dt ¼ 0, (55)
V$jdm  RT0/Ft þ dE/dt ¼ 0, (56)
where jE is the internal convective current density and jdm is the
migration current density. Eq. (55) is the governing equation for the
electric current density in electrochemical reactions, and Eq. (56) is
the migration equation.
Eq. (55) is the extension of current density conservation:
V$jdd þ (1/v) vjdd/vt ¼ 0 (57)
where va ¼ l/t is the average particle velocity. Note that jE leads to
jdd in the absence of internal convection. Eq. (57) is the transform of
the continuity equation
V$jdd þ q vne/vt ¼ 0
where ne is the number density and q is the electric change per
particle.
The second term in the left hand side of Eq. (55) represents the
electrochemical reaction which reflects the internal convective
electrochemical mechanism and is useful to demonstrate polari-
zation mechanisms. Eq. (55) is analyzed under the assumption of
constant temperature and constant pressure in which the system is
electrochemically isolated from its surroundings.
8.1. Non-equilibrium electrochemical reactions: the processes of
(nonzero ze)
We have the differential equation for non-equilibrium electro-
chemical reaction (55). Using the method of separation of variables
for the current density
jE (E, t, r) ¼ j(Е) B(t) A(r),
we derive the following three differential equations from Eq. (55):
vj/vE þ (zeF/RT0) j(Е) ¼ 0, (58)
vB/vt þ (b /t) B(t) ¼ 0, (59)
V$A þ k A(r) ¼ 0. (60)
 H.-S. Roh / Energy xxx (2015) 1e21 11

The three constants ze, b, and k in the separation of variables are l V$jE  (RT0/F) vjE/vЕ ¼ 0. (67)
introduced, and their relation is given by
The current density then takes the form:
z2e þ k2  b2 ¼ 0
0
jE (EP, rB) ¼ j0 exp (zeFEP/RT0) exp (k$rB/l)
where the constants denote:
0
where j0 ¼ j0A0 and k2 ¼ z2e .
ze: the electrochemical particle number constant,
b: the temporal particle number constant,
8.2. Irreversible quasi-equilibrium electrochemical reactions: the
k: the spatial particle number constant.
processes of (zero ze or zero EP)
ze ¼ nNa in Eq. (58) is the charge particle number constant and n is
During irreversible quasi-equilibrium electrochemical reactions,
the mole number of the charge particles. kr ¼ b/t ¼ 1/t0 in Eq. (59)
two processes are possible to occur:
stands for the rate constant in electrochemical reactions and is the
Migration with b2 ¼ k2 (nonzero b and k; ze ¼ 0),
inverse of the mean reaction time t0. k ¼ (b2  z2e )1/2 ¼ l/l0 in Eq.
Concentration diffusion with b2 ¼ z2e þ k2 (nonzero b and k;
(60) is connected to the reaction cross section sc ¼ V/kl0, and
EP ¼ 0).
n0 ¼ k/V is the particle number per unit volume.
In quasi-equilibrium process, the governing equation becomes
Then the three integrated solutions for (58), (59), and (60) are
obtained respectively:
l V$gd þ t vgd/vt ¼ 0.
P 0 P
j(Е ) ¼ j exp (zeFE /RT0), (61)
In the absence of the internal convection source (zero ze), the
B 0 B governing process is migration with constant particle number. The
B(t ) ¼ B exp (bt /t), (62)
homogeneous migration equation for an isotropic process reduces
to
A(rB) ¼ A0 exp (k$rB/l), (63)
DEV2E  vE/vt ¼ 0 (68)
where k ¼ kn ¼ (b2  z2e )1/2n and n is the unit vector in the diffusion
direction of the current density. Eq. (61) has the form of the
where DE ¼ 1/m0s is the migration coefficient and s ¼ neq2t0/m is
Arrhenius type equation.
the electric conductivity. The condition for the constants is b2 ¼ k2.
Eqs. (61)e(63) describe the electric potential dependence,
In the absence of the internal convection source (zero
temporal dependence, and spatial dependence of the current
EP ¼ jE  E0j), the governing process is the concentration diffusion
density, respectively. When the initial and boundary conditions are
with constant electric potential. The homogeneous diffusion
applied, the excess forms of the electric potential, time, and
equation for an isotropic process becomes
displacement variables relative to their relative equilibriums are
utilized in Eqs. (61)e(63), respectively:
D0V2 C  vC/vt ¼ 0. (69)
P 0
E ¼ jEeE j,
The relation for the constants is b2 ¼ k2.
tB ¼ t  t0,
rB ¼ jr  r0jn. (64)
8.3. Equilibrium electrochemical reactions: the process of (nonzero
The current density is then found to be the form: ze, b, and k; E ¼ 0)
0
jE (EP, tB, rB) ¼ j0 exp (zeFEP/RT0) exp (btB/t) exp (k$rB/l) (65) The equilibrium process takes place at a nonzero E0 ¼ jEp0  Er0j;
0
E ¼ 0 in Eq. (64). Note that E0 is a variable depending on the electric
where j0 ¼ j0B0A0. potential difference between Ep0 and Er0 while E0 is the equilibrium
In non-equilibrium electrochemical reactions for nonzero ze, the potential. Similarly, the spatial and temporal equilibriums are
Gibbs energy change is not zero: nonzero DG. Two special processes attained at t ¼ r ¼ 0 in (64), but t0 and r0 are nonzero variables.
are possible: The equilibrium variables are the relative electric potential,
Unsteady and uniform electrochemical reactions with time, and displacement and can be parameterized as
z2e  b2 ¼ 0 (nonzero ze, EP and b; k ¼ 0),
Non-uniform and steady electrochemical reactions with E0 ¼ jEp0  Er0j ¼ jEeE0j,
z2e þ k2 ¼ 0 (nonzero ze, EP, and k; b ¼ 0).
The governing equation for unsteady and uniform electro- t0 ¼ tp0  tr0 ¼ t  t0,
chemical reactions is found to be
r0 ¼ jrp0  rr0jn ¼ jr  r0jn.
(RT0/F) vjE/vЕ  t vjE/vt ¼ 0. (66)
Under the parameterization, the governing equation for equi-
The current density then reduces to the form: librium electrochemical reactions leads to
0
jE (EP, tB) ¼ j0 exp (zeFEP/RT0) exp (btB/t) lV$j0  (RT0/F) vj0/vЕ þ t vj0/vt ¼ 0. (70)

0
where j0 ¼ j0 B0 and b2 ¼ z2e . Using the method of separation of variables, we find governing
equations from (70):
In this case of non-uniform and steady electrochemical re-
actions, the governing equation becomes vj0/vЕ  (zeF/RT0) j0 (Е) ¼ 0, (71)

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12 H.-S. Roh / Energy xxx (2015) 1e21
vB0/vt  (b/t) B0 (t) ¼ 0,
V$A0  k A0 (r) ¼ 0,
where the separation variable constants have the relation:
z2e þ k2  b2 ¼ 0.
Applying initial and boundary conditions, we obtain the equi-
librium convection current densities from (71)e(73):
0 0 0
j(Е ) ¼ j exp (zeFE /RT0),
B(t0) ¼ B0 exp (bt0/t),
A(r0) ¼ A0 exp (k$r0/l).
Eqs. (74)e(76) satisfy the initial and boundary conditions. Note
that Eqs. (61)e(63) lead to Eqs. (74)e(76) at E ¼ t ¼ r ¼ 0,
respectively. The current density then reduces to the final form:
0
j0 (E0, t0, r0) ¼ j0 exp (zeFE0/RT0) exp (bt0/t) exp (k$r0/l)
0
where j0 ¼ j0 B0 A0.
The activation potential Ea, activation time ta, and activation
displacement ra are respectively defined by the maximum values in
magnitude:
Ea ¼ jEp0 e Er0jmax ¼ jE e E0jmax,
ta ¼ jtp0 e tr0jmax ¼ jt e t0jmax,
ra ¼ njrp0 e rr0jmax ¼ njr e r0jmax.
The integrated solutions of (74)e(76) satisfy j0(Е0 ¼ 0) ¼ j0,
B0(t0 ¼ 0) ¼ B0, and A0(r0 ¼ 0) ¼ A0 at the initial conditions of
E0 ¼ 0, t0 ¼ 0, and r0 ¼ 0, which stand for electrochemical, tem-
poral, and spatial equilibriums. Furthermore, they satisfy
j0(Е0 ¼ Еa) ¼ j1, B0(t0 ¼ ta) ¼ B1, and A0(r0 ¼ ra) ¼ A1 at the limiting
conditions of E0 ¼ Еa, t0 ¼ ta, and r0 ¼ ra. A variable with the
subscript a indicates the threshold value, and an amplitude variable
with the superscript 1 denotes its limiting value. Using the initial
and limiting conditions, we can obtain the following relations:
ze ¼ (RT0/FEa) ln (j1/j0),
b ¼ (t/ta) ln (B1/B0),
k ¼ (l/ra) ln (A1/A0).
From (74), the electric potential becomes
E ¼ E0 þ (kBT0/zeq) ln Z0g
which produces the Nernst equation in an equilibrium electro-
chemical reaction:
E ¼ E0 þ (RT0/nF) ln K0.
8.4. Reversible quasi-equilibrium electrochemical reactions: the
process of (nonzero b and k; ze ¼ E ¼ 0)
Reversible quasi-equilibriums are the convection electro-
chemical reactions of (nonzero b and k; ze ¼ t ¼ r ¼ 0 or
EP ¼ t ¼ r ¼ 0). The spatial and temporal equilibriums are attained
at t ¼ r ¼ 0 in (64), but t0 and r0 are nonzero variables. The gov-
erning equation becomes
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(72) lV$jv þ t vjv/vt ¼ 0. (80)
(73) The particle number constants have a relation:
k2  b2 ¼ 0.
The current density is thus of the final form:
0
jv (t0, r0) ¼ j0 exp (bt0/t) exp (k$r0/l)
0
where j0 ¼ B0 A0.
(74) Eq. (80) leads to the particle number conservation (nonzero b
and k; ze ¼ t ¼ r ¼ 0):
(75)
vC/vt þ V$(Cva) ¼ 0.
(76)
This reduces to the conservation of convective electric charge or the
conservation of convective mass (the continuity equation):
V$jv þ q vne/vt ¼ 0
(77) where jv ¼ qneva. The conservation of electric potential is given by
vE/vt þ va$VE ¼ 0.
9. Chemical reactions and electrochemical reactions
The chemical energy transfer theory of chemical reactions
provides accurate information about the chemical potential,
(78) displacement, and time dependence of chemical reactions. In
chemical reactions, the energy difference of reactants and products
is obtained in the chemical potential dependence, the reaction
cross section is given in the spatial dependence, and the reaction
rate is found in the temporal dependence. The Arrhenius equation
is derived from Eq. (48). At the activation chemical potential ma,
position ra, and time ta,
g1(m) ~ g0 (bta/t)(kra/l) exp (nma/kBT0).
After removing constants, the Arrhenius equation for the rate
constant can be given by
kr ¼ (bk/va) exp(Q/RT0) ¼ kr0 exp (Q/RT0)
where kr0 ¼ bk/va is the frequency factor which depends on the
reaction frequency and steric factor,
Q ¼ nmaNA ¼ nNAjmp0  mr0jmax is the activation energy, and
exp(Q/RT0) reflects the fraction of collision with sufficient energy
to produce a chemical reaction.
Fig. 5(a) and Fig. 5(b) respectively show the Gibbs energy flux
and the current density profiles during equilibrium processes. The
Gibbs energy flux and the electric current density are respectively
g0(m0) ¼ g0 exp (nm0/kBT0),
(79)
j0(Е0) ¼ j0 exp (zeFE0/RT0).
The Gibbs energy flux at the global equilibrium chemical m0
leads to the exchange chemical energy flux, and the current density
at the equilibrium electric potential E0 reduces to the exchange
current density: g0(m0) ¼ g0 and j0(Е0) ¼ j0. The limiting Gibbs
energy flux at the equilibrium process
g1(ma) ¼ g0 exp (nma/kBT0)
 H.-S. Roh / Energy xxx (2015) 1e21 13

Similarly, the Gibbs energy flux is drawn as a function of

Fig. 5. Gibbs energy flux and current density. The activation chemical potential and
electric potential are measured from their global equilibriums of m0 and E0, respec-
tively. (a) Gibbs energy flux profile as a function of chemical potential during an
equilibrium process. The equilibrium process occurs in the regime of 0 < m0 < ma or
m0 < m < (m0þma). (b) Current density profile as a function of electric potential during an
equilibrium process. The equilibrium process occurs in the regime of 0 < E0 < Ea or
E0 < E < (E0þEa).
is attained at the activation chemical potential ma which is the
maximum chemical potential of m0 ¼ jmp0  mr0j ¼ jm  m0j. The
activation chemical potential is associated with the work function
difference between reactants and products. It is connected to the
equilibrium constant Z01 1 0
g ¼ g /g :
ma ¼ (kBT0/n) ln Z01
g .
displacement. Fig. 6(a) and (b) respectively represent the chemical
energy flux and current density profiles in convection mechanisms
until the reversible convection processes reach the initiation dis-
placements of the irreversible quasi-equilibrium migration pro-
cesses. The spatial chemical energy flux gap at the activation
displacement is connected to the spatial particle number constant
k. Once the process reaches the activation displacement, the
nonzero k diffusion process occurs.
We recognize that there are four chemical energy transfer re-
gions of internal thermodynamic space and external space as
depicted in Figs. 5 and 6. The chemical energy transfer regions
consist of internal equilibrium, internal convection, external con-
vection, and external diffusion. Internal convection is the irre-
versible non-equilibrium process, and external convection is the
reversible quasi-equilibrium process. Therefore, the chemical en-
ergy transfer theory presents the Gibbs energy fluxes produced by
the internal equilibrium and internal convective chemical reactions
as well as external convective and external diffusion chemical re-
actions. The four regions have categorical constraint conditions
illustrated in Tables 2, 4 and 5.
The chemical energy transfer theory predicts broken discrete
symmetries at the activation points of the irreversible processes
transferred from the reversible processes:
Chemical potential reversal symmetry breaking at the activation
chemical potential ma,
Space reversal symmetry breaking at the activation displace-
ment ra,
Time reversal symmetry breaking at the activation time ta.
Discrete symmetries are broken, and certain preferred di-
rections are chosen during the irreversible chemical processes. At
the activation chemical potential, the reversible equilibrium pro-
cess is changed to the irreversible non-equilibrium process. The

ma is positive for a spontaneous reaction and negative for a

nonspontaneous reaction.

We determine that at the activation chemical potential ma, there

is the Gibbs energy flux gap between the limiting energy flux g1 at
the chemical valence band and the exchange energy flux g0 at the
chemical conduction band. Before an external chemical potential is
applied, the system is in the equilibrium process with the exchange
Gibbs energy flux g0. An applied external chemical potential is
utilized to make the equilibrium process proceed until the chemical
potential reaches the activation chemical potential. At the activa-
tion chemical potential, the equilibrium process reaches the
limiting Gibbs energy flux g1 as shown in Fig. 5(a). The chemical
energy flux gap and the chemical energy gap between the equi-
librium and non-equilibrium processes at the activation potential
ma are dependent on the particle number constant n:

Gibbs energy flux gap: Dg ¼ g1 e g0,

Gibbs energy gap: DG ¼ nma.

Phase transitions caused by chemical energy transfer present

first order phase transitions since they are accompanied by
discontinuous particle number gaps at activation chemical poten-
tials. The order parameter for the phase transitions is the chemical
potential change in regions of the internal equilibrium and internal
convection. Particle pairing (or dissociation) mechanisms appear at
activation chemical potentials.
Fig. 6. Gibbs energy flux and current density in the regime of 0 < r0 < ra or
r0 < r < (r0þra). The activation displacement is measured from its global equilibrium
r0. (a) Gibbs energy flux profile as a function of displacement during a convection
process. (b) Current density profile as a function of displacement during a convection
process.

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14 H.-S. Roh / Energy xxx (2015) 1e21
governing Eq. (41) for equilibrium is different from the governing
Eq. (23) for non-equilibrium. At the activation displacement, the
reversible convection process is transformed to the irreversible
diffusion process. The governing Eq. (51) for convection leads to the
governing Eq. (38) for diffusion. The particle number constants n
and k change their front positive-negative signs as the indices of
energy flux exponential functions at their corresponding activation
values.
From Table 5, we analyze that the intensive and extensive var-
iables of chemical potential and particle number are conserved
properties during the processes of internal equilibrium and con-
vection. However, they are not conserved properties during the
processes of internal convection and diffusion. We have known that
the second law of thermodynamics is the entropy increase princi-
ple. According to irreversible quasi-equilibrium Eqs. (36) and (37),
we recognize that the particle number increase principle and the
chemical potential decrease principle are analogous to the entropy
increase principle.
Fig. 7(a) shows the Gibbs energy flux profiles of internal equi-
librium and external convection as a function of chemical potential
and space in chemical reactions. Along the two perpendicular axes
of m and g, the reversible convective processes occur while the in-
ternal equilibrium process takes place in the intermediate area
between the two extreme convective processes. The two reversible
convective processes contain unsteady, temporal contributions as a
function of space. We expect similar statements for the current
density profiles of internal equilibrium and external convection as a
function of electric potential and space in electrochemical re-
actions, as shown in Fig. 7(b). Along the two perpendicular axes of E
and j, the reversible convective processes takes place while the
internal equilibrium process proceeds in the intermediate area
between the two extreme convective processes.
We schematically obtain the energy flux profiles of internal
convective and external diffusive mechanisms as shown in Fig. 8.
Fig. 8(a) represents the Gibbs energy fluxes of chemical reactions as
a function of chemical potential and space. Fig. 8(b) reflects the
current densities of electrochemical reactions as a function of
Fig. 7. Energy flux profiles of internal equilibrium and external convection reactions.
(a) Gibbs energy fluxes as a function of chemical potential and space in chemical re-
actions. (b) Current densities as a function of electric potential and space in electro-
chemical reactions.
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equilibrium chemical reactions, Energy (2015), http://dx.doi.org/10.1016/j.energy.2015.06.049
electric potential and space. Along the two perpendicular axes of m
and g or E and j, the irreversible diffusive processes such as the
migration and diffusion process take place while the internal
convective process advances in the intermediate area between the
two extreme conductive processes. The diffusive processes contain
unsteady, temporal contributions as a function of space while the
internal convective processes include both steady and unsteady
contributions as a function of space.
Fig. 9 schematically illustrates the four diffusion processes of
chemical reactions and electrochemical reactions in the absence of
internal convective energy transfer. Eqs. (39) and (40) respectively
reflect the migration and concentration diffusion processes in
quasi-equilibrium chemical energy transfer. Eqs. (68) and (69)
respectively depict the constant charge (migration) and constant
electric potential (diffusion) processes in quasi-equilibrium elec-
trochemical energy transfer.
Gibbs energy transfer between the equilibrium and convection
processes takes place under the relation (98) among the particle
number constants, and Gibbs energy transfer between the internal
convection and diffusion processes also arises under the require-
ment (98). The equilibrium and convection processes governed by
Eq. (41) are reversible while the internal convection and diffusion
processes governed by Eq. (23) are irreversible. The particle num-
ber constant n represents the chemical energy transfer between the
thermodynamic spaces and the conventional space and time.
The chemical energy fluxes in chemical energy transfer are
categorized into six modes:
g ¼ gdd þ gdm þ gv þ gm þ g0 þ gr
where gdd is the diffusion chemical energy flux due to the con-
centration gradient VC,
gdm is the migration chemical energy flux due to the chemical
potential gradient Vm,
Fig. 8. Energy flux profiles in internal convection and external diffusion energy
transfer mechanisms. (a) Gibbs energy fluxes as a function of chemical potential and
space in chemical reactions. (b) Current densities as a function of electric potential and
space in electrochemical reactions.
 H.-S. Roh / Energy xxx (2015) 1e21 15

MaxwelleBoltzmann distribution: Zg ¼ Pi zNa

gi /Ni!,

BoseeEinstein distribution: Zg ¼ Pi zNa

gi ,

FermieDirac distribution: Zg ¼ Pi zNa

gi ,

where the reaction activation satisfies the required rule for indi-
vidual particle distribution. If the de Broglie wavelength

lT ¼ (h2f /2pmkBT0)1/2

is small compared with the interparticle wave length, particles in

Fig. 9. Energy diffusion processes in the absence of internal convection. (a) Chemical the system obey MaxwelleBoltzmann statistics. Otherwise, Bose-
reactions. (b) Electrochemical reactions.
Einstein statistics or FermieDirac statistics is more appropriate.
Equilibrium chemical energy transfer and electrochemical en-
ergy transfer are represented as two Eqs. (50) and (79), respectively.
gv is the convective chemical energy flux,
gm is the internal convective chemical energy flux due to the m ¼ m0  (RT0/n) ln K0,
chemical potential change Dm,
g0 is the internal equilibrium chemical energy flux due to the E ¼ E0  (RT0/zeF) ln K0.
equilibrium change m0,
and gr is the radiant chemical energy flux. In non-equilibrium, the two intensive variables play essential roles
in chemical reactions and electrochemical reactions.
The internal convective chemical energy flux gm is generated in the
internal phase space of chemical potential while the diffusion en- m ¼ m0  (kBT0/n) ln Zg,
ergy fluxes are created by the conductive diffusion and migration
processes. The two diffusive chemical energy fluxes of migration E ¼ E0  (kBT0/zeF) ln Zg.
and diffusion chemical energy are coupled more or less in phase
transitions. The diffusive chemical energy fluxes do not contribute The two equations lead to the same form
to the chemical energy flux profile as a function of chemical po-
tential even though they are closely related to the activation G ¼ G0 þ kBT0 ln Zg
chemical potentials of chemical energy fluxes.
The Gibbs reaction quotient Zg can be defined by an extension of since Zg ¼ KNa. The relative time and displacement are similarly
the Gibbs free energy G in analogy to the Gibbs partition function expressed as
Z0 ¼ kBT0 ln G0 in statistical mechanics:
t ¼ t0  (t/b) ln Ztg,
N
Zg ¼ exp (DG /kBT0).
r ¼ r0  n(l/k) ln Zrg,
At equilibrium, an equilibrium Gibbs transfer function is also
defined: where Ztg ¼ gt/g0t and Zrg ¼ gr/g0r.

Z0g ¼ exp (DG0/kBT0).

Using the above two equations, we have the actual Gibbs energy
transfer and the equilibrium Gibbs energy transfer:
DG ¼ DG0 þ kBT0 ln Zg ¼ kBT0 ln (Zg/Z0g),
DG0 ¼ G0p  G0r ¼ kBT0 ln Z0g ¼ kBT0 ln (Z0p/Z0r),
10. Chemical energy transfer mechanisms in non-equilibrium
chemical reactions
The chemical energy transfer theory can be utilized to explore
non-equilibrium chemical energy transfer processes. We can
readily name several chemical reactions [27e29] belonging to these
categories:

where G0p ¼ kBT0lnZ0p and G0r ¼ kBT0 lnZ0r are the equilibrium H2 þ I2 ——————> 2HI,
Gibbs free energies for products and reactants, respectively, and Z0p
and Z0r are the conventional Gibbs partition functions of products H2 þ Br2 ——————> 2HBr,
and reactants, respectively. The Gibbs reaction quotient can be
connected to the reaction quotient in chemical reactions: Zg ¼ KNa. H2 þ Cl2 ——————> 2HCl,
The conventional Gibbs partition function in statistical mechanics
can thus be related to the activity: 2H2 þ O2 ——————> 2H2O,

Z0p ¼ (a0p)Na 2NO þ O2 ——————> 2NO2,

where a0p denotes the equilibrium activity of products.
The Gibbs reaction quotient can also be expressed for sub-
systems with i species. In this case, we introduce the Gibbs reaction
activation zgi for a particle with species i. Then the reaction quo-
tients for different statistical distributions reduce to:
C2H6 ——————> C2H4 þ H2.
Non-equilibrium chemical energy transfer processes are
described at the interface of solid and liquid, as shown in Fig. 10(a).
In the presence of an external chemical energy ge, the differential

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16 H.-S. Roh / Energy xxx (2015) 1e21
Fig. 10. (a) Interface of solid and liquid. (b) Spatial cylindrical coordinates and the
spatial particle number constant k. (c) Gibbs potentials at the solideliquid interface.
equation for the chemical energy flux in chemical reactions takes
the following form from Eq. (24):
ge ¼ g þ (kBT0/n)dg/dm.
In the cylindrical coordinates of r, f, and z, as shown in Fig. 10(b),
the chemical energy flux g and the chemical potential m depend on r
and z since g and m are symmetric in the azimuthal angle f. The
Gibbs potentials for a chemical reaction are depicted in Fig. 10(c). Q
is the activation energy of a chemical reaction. The reactions are
spontaneous if the Gibbs potential energy difference DG is negative.
A chemical reaction is dependent on the applied Gibbs energy flux
or chemical potential which changes the Gibbs energies in reaction
coordinates.
Fig. 11 shows the Gibbs energy flux profiles as a function of
chemical potential during equilibrium and non-equilibrium pro-
cesses in the presence of external chemical potential. The reversible
and irreversible Gibbs energy fluxes respectively take the forms:
g0(m0) ¼ g0 exp (nm0/kBT0),
N 1
g(m ) ¼ g [1  exp (nm /kBT0)].N
An externally applied chemical potential initiates to make an
equilibrium process proceed until the chemical potential reaches
the activation chemical potential. Before the external chemical
potential is applied, the system is in the equilibrium process with
the exchange Gibbs energy flux g0. At the activation chemical po-
tential ma, the equilibrium process gains the limiting Gibbs energy
flux g1 as shown in Fig. 11. The chemical energy flux gap between
the equilibrium and non-equilibrium processes depends on the
particle number constant n. Above the activation chemical poten-
tial, a non-equilibrium process proceeds from the exchange Gibbs
energy flux g0 toward the limiting Gibbs energy flux g1. The non-
equilibrium process is an irreversible process, and the limiting
Gibbs energy flux in equilibrium plays the role of an internal Gibbs
energy flux so that the non-equilibrium process eventually rises to
the limiting Gibbs energy flux as the excess chemical potential
increases. The limiting Gibbs energy flux g1 is determined by the
equilibrium process caused by the Gibbs energy difference
Fig. 11. Gibbs energy flux profiles as a function of chemical potential during the
equilibrium process of m0 < m < (m0 þ ma) and the non-equilibrium process of
m > (m0 þ ma) in the presence of external chemical potential. The activation chemical
potential is measured from its global equilibrium m0.
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DG0 ¼ (Gp0 e Gr0) between chemical reactants and products. Note
that the limiting Gibbs energy flux g1 is identical with the external
Gibbs energy flux ge in Eq. (81).
We define the activation chemical potential ma, the activation
time ta, and the activation distance ra, respectively, as the
maximum values in their magnitudes:
p
ma ¼ jm0 e mr0jmax ¼ jm e m0jmax,
p
ta ¼ jt0 e tr0jmax ¼ jt e t0jmax,
p
ra ¼ jr0 e rr0jmax ¼ jr e r0jmax.
The particle number constants are found to be
(81)
n ¼ (kBT0/ma) ln (g1/g0),
b ¼ (t/ta) ln (B1/B0),
k ¼ (l/ra) ln (A1/A0),
where g0 is the exchange Gibbs energy flux and g1 is the limiting
Gibbs energy flux.
The relativistic relation among the particle number constants is
determined by
n2 þ k2  b2 ¼ 0.
When we apply the restriction to chemical reactions, we classify the
following three non-equilibrium regimes:
n2 ¼ b2 > 0 and k2 ¼ 0 for activation reactions,
n2 ¼ b2  k2 > 0 for concentration reactions,
n2 ¼ b2  k2 < 0 for transition reactions.
Moreover, the process conversion from non-equilibrium to equi-
librium takes place in transition reactions:
n2 ¼ b2  k2 > 0 for transition reactions,
n2 ¼ b2  k2 < 0 for film reactions.
Stable conditions for a process are given by
n2 > 0 for chemical stability,
b2 > 0 for temporal stability,
k2 > 0 for spatial stability.
In the chemical energy transfer processes at the interface of
solid and liquid, Fig. 12(a) depicts the four control regimes formed
by the pure chemical reaction processes: activation, concentration,
transition, and film reactions. The four regimes are analogous to the
four regimes designed in the polarization processes of electro-
chemical reactions, as shown in Fig. 12(b) [32]. There are three
reaction barriers which depend on chemical potential, space, and
time. It implies that the three variables play the roles of the reaction
coordinates. The reaction barriers exist between the layers of
concentration and transition reactions. Fig. 12(a) shows two
opposite chemical energy fluxes in concentration and transition
chemical energy transfer. The chemical energy flux by reactants is
larger than the chemical energy flux by products in concentration
chemical energy transfer while the chemical energy flux by prod-
ucts is larger than the reactant chemical energy flux in transition
chemical energy transfer. In concentration chemical energy trans-
fer, the chemical energy flux by reactants governs while in film
chemical energy transfer, the chemical energy flux by products
 H.-S. Roh / Energy xxx (2015) 1e21
Fig. 12. Four control regimes formed by reaction processes. (a) Chemical reactions. (b)
Polarization in electrochemical reactions.
governs. There are a maximum limiting energy flux in the con-
vection mechanism, a maximum energy flux in the concentration
mechanism, two maximum and minimum limiting chemical fluxes
in the transition mechanism, and a minimum limiting energy flux
in the film mechanism.
We here concentrate on the application of Eq. (81) to non-
equilibrium chemical reactions. As Fig. 12 shows, the probable
behavior of chemical energy flux in the nonzero modes of n in a non-
equilibrium chemical reaction can be predicted as a function of excess
chemical potential mN ¼ jmw e (m0 þ ma)j where ma is the activation
chemical potential. In each chemical energy transfer regime of the
four distinct regimes, the particle number constant n plays the
important role in characterizing the chemical energy flux. The zero n
is relevant to the difussive chemical energy flux, and the nonzero n is
connected to the internal convective chemical energy flux.
In the presence of external chemical energy ge, Eq. (81) leads to
the differential equation in the four distinct regimes:
ge ¼ g þ kBT0 [(1/na)dgA/dmþ(1/nc)dgC/dm
 (1/nt)dgT/dm  (1/nf)dgF/dm].
The second term in the right hand side of (82) includes the four
mechanisms of the chemical reactions. The four mechanisms are
additive in the chemical energy flux which is proportional to
chemical potential difference. The total chemical energy flux is thus
expressed as the sum of the parallel chemical energy fluxes:
g ¼ gA þ gC þ gT þ gF.
In a process dominated by activation chemical energy, the dif-
ferential equation for the chemical energy flux leads to
geA ¼ gA þ (kBT0/na) dgA/dm
where ge is the applied chemical energy flux to the solid wall.
Solving Eq. (84), we find the chemical energy flux by convection
chemical energy, gA, given as a function of the excess chemical
potential mA:
gA ¼ g1A [1 e exp (namA/kBT0)]
where g1A ¼ geA. The limiting Gibbs energy flux at the activation
chemical potential of activation reaction maa is determined at the
end of the equilibrium process:
g1A ¼ g0 exp (namaa/kBT0).
We may apply the analogous schemes to the four control
mechanisms and establish the total Gibbs energy flux in an equa-
tion [30e36]. The total chemical energy flux can approximately be
given by the sum of chemical energy fluxes in the four chemical
reaction regimes:
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17
g ¼ g1A [1  exp (namA/kBT0)] þ g1C [1  exp (ncmC/kBT0)]
þ [g1C exp (nat mT/kBT0) H(mtr  m) þ g1Fexp (nbt mF/kBT0)
H(mtr  m)] þ g1F exp (nfmF/kBT0) (86)
where H is the Heaviside step function. The transition chemical
potential is expressed as
mtr ¼ [1/(nbt  nat )] [(nbt maf  nbt mat) þ ln(g1C/g1F)].
The first term in the right hand side represents the Gibbs energy
flux due to activation chemical energy, the second the Gibbs energy
flux due to concentration, the third the Gibbs energy flux in tran-
sition chemical energy, and the fourth the Gibbs energy flux in film
chemical energy. g1A, g1C, and g1F respectively indicate the limiting
Gibbs energy fluxes in activation, concentration, and film chemical
reactions.
We get the excess chemical potentials from the absolute acti-
vation chemical potentials in the four mechanisms:
mA ¼ jmw e (m0 þ maa)j,
mC ¼ jmw e (m0 þ mac)j,
mT ¼ jmw e (m0 þ mat)j,
mF ¼ jmw e (m0 þ maf)j, (87)
where m0 is the saturation chemical potential and mw is the wall
chemical potential. The activation chemical potentials of maa, mac,
mat, and maf relative to the global equilibrium chemical potential m0
are positive quantities in chemical reactions.
In terms of (86), the chemical potential m in each chemical re-
action mechanism can be summarized as
m ¼ m0 þ maa  (kBT0/na) ln ZAge, m ¼ m0 þ mac  (kBT0/nc) ln ZCge,
(82)
m ¼ m0 þ mat þ (kBT0/nt) ln ZTge, m ¼ m0 þ maf þ (kBT0/nf) ln ZFge, (88)
where Zge ¼ 1  gm/g1m in the activation or cencentration chemical
reaction, Zge ¼ gm/g1m in the transition or film chemical reaction, and
the limiting chemical energy flux g1m depends on chemical poten-
tial. Fig. 13 demonstrates schematic chemical energy fluxes as a
function of excess chemical potential. The control mechanisms are
(83) presented, and the maximum limiting state of concentration re-
action is regarded as an intermediate transition state.
Schematic diagrams for chemical energy transfer mechanisms of
activation and concentration chemical energy in chemical reactions
are sketched in Fig. 14. The activation chemical energy process is a
(84) slow, stable, and irreversible mode and the concentration chemical
energy process is a fast, stable, and irreversible mode. The former is
the process with a single phase while the latter is the process with
the two phase components. They have different initiation chemical
potentials depending on conductive chemical energy processes.
The chemical energy transfer theory thus predicts multi-step
reaction processes. For example, we can consider the hydro-
(85) geneiodine reaction. During an activation reaction, a bimolecular
reaction takes place:
H2 þ I2 ——————> 2HI. (89)
During concentration and transition reaction, termolecular reaction
(or three body association reaction) proceeds:
I2 ——————> 2I,
H2 þ 2I ——————> 2HI. (90)
The reaction speed of the process (89) is slow, and the Gibbs energy
change during the process is small. On the other hand, the reaction
18 H.-S. Roh / Energy xxx (2015) 1e21

Fig. 13. Schematic chemical energy fluxes as a function of excess chemical potential. (a) Nonspontaneous transition chemical reactions. (b) Spontaneous transition chemical
reactions.

speed of (90) is fast, and the Gibbs energy change during the pro- tA ¼ t e (t0 þ taa),
cess is large. The process (90) is analogous to the transition in the tC ¼ t e (t0 þ tac),
transition state theory [10e12], and the maximum limiting state of tT ¼ t e (t0 þ tat),
concentration reaction corresponds to the transition state. Hydro- tF ¼ t e (t0 þ taf), (94)
genebromine reaction, hydrogenechlorine reaction, hydro-
geneoxygen reaction, and decomposition of nitrogen pentoxide where t0 is the global equilibrium time. taa, tac, tat, and taf are the
reaction are the analogous multi-step processes. activation times for the four chemical reaction mechanisms. The
In the presence of the external chemical energy flux ge, the time in each chemical reaction mechanism is expressed as
temporal chemical energy transfer Eq. (25) yields
t ¼ t0 þ taa  (t/ba) ln MA e,
ge ¼ g þ (t/b) dg/dt (91) t ¼ t0 þ tac  (t/bc) ln MCe ,
t ¼ t0 þ tat þ (t/bt) ln MTe,
where t is the mean reaction time. From Eq. (91), the temporal t ¼ t0 þ taf þ (t/bf) ln MFe, (95)
chemical energy flux has the integrated solution
where Me ¼ 1  gt/g1t in the activation or cencentration temporal
g (tB) ¼ g1t [1 e exp (btB /t)]. (92) chemical reaction, Me ¼ gt/g1t in the transition or film temporal
chemical reaction, and the limiting chemical energy flux g1t de-
We combine (86) and (92) and then find the chemical energy flux in
pends on time. Since the temporal particle number constant bc in
activation chemical energy and concentration chemical energy
activation reactions is less than bn in concentration reactions, the
transfer:
chemical process in activation reactions is slower than that in
g(m,t) ¼ g1A [1 e exp (namA/kBT0)] [1 e exp (ba tA/t)] concentration reactions.
Spatial behavior for the chemical energy flux is understood by
þ g1C [1 e exp (ncmC/kBT0)] [1 e exp (bc tC/t)] (93) changing Eq. (26). In the presence of an external source we, it is
modified as
where the temporal particle number constant ba in activation re-
actions is less than the temporal particle number constant bc in ge ¼ V$g þ (k/l) g (r). (96)
concentration reactions, and the diffusion process in activation
reactions is slower than that in concentration reactions. Eq. (96) has the integrated solution
The excess times in the four chemical reaction mechanisms
indicate g (rB) ¼ g1r [1 e exp ((k/l) n$rB)]
¼ g1r [1 e exp (((n2  b2)1/2/l) rB cos q)] (97)

where q is the angle between the vectors of n and z: ((n2  b2)1/2/l)

n$rB ¼ k zB cosq/l and tan q ¼ kr/kz.
We find the excess distances along the z axis in the four
chemical reaction mechanisms:

zA ¼ jz e (z0 þ zaa)j,
zC ¼ jz e (z0 þ zac)j,
zT ¼ jz e (z0 þ zat)j,
zF ¼ jz e (z0 þ zaf)j, (98)

where z0 is the boundary position in global equilibrium. zaa, zac, zat,

and zaf are the activation distances for the four chemical reaction
Fig. 14. Chemical energy transfer mechanisms. (a) As a function of chemical potential.
mechanisms. The distance in each phase transition mechanism is
(b) As a function of distance. indicated as

Please cite this article in press as: Roh H-S, Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and
equilibrium chemical reactions, Energy (2015), http://dx.doi.org/10.1016/j.energy.2015.06.049
 H.-S. Roh / Energy xxx (2015) 1e21
z ¼ z0 þ zaa,
z ¼ z0 þ zac þ (l/kc) ln LCe ,
z ¼ z0 þ zat  (l/kt) ln LTe,
z ¼ z0 þ zaf  (l/kf) ln LFe, (99)
where Le ¼ 1  gz/g1z in the cencentration spatial chemical reac-
tion, Le ¼ gz/g1z in the transition or film spatial chemical reaction,
and the limiting chemical energy flux g1z depends on distance. The
layer in activation chemical reactions is uniform spatially,
compared with the other layers.
Summarizing the above descriptions, we draw Fig. 15 which
demonstrates the schematic diagrams of the chemical energy
fluxes as a function of excess chemical potential, time, and distance
in the four regimes of chemical reactions.
11. Discussions
Chemical energy is the ubiquitous form of available energy
which is the potential of a chemical substance to undergo a
transformation through a chemical reaction. There are vital ad-
vantages of using chemical energy in multi-disciplinary fields.
Compared to other energy source, chemical energy sources are
abundantly available. They are easily combustible, providing
instant energy in the form of heat, and their combustion efficiency
is relatively high. In the following, a few broad scopes of the pro-
posed chemical theory are addressed.
Chemical energy transfer can be utilized along with other
thermodynamic energy transfer mechanisms. Thermodynamic
energy transfer consists of internal energy transfer, heat transfer,
Fig. 15. Schematic diagrams of the chemical energy flux in the four regimes of
chemical reactions. (a) As a function of excess chemical potential. (b) As a function of
time. (c) As a function of distance.
Please cite this article in press as: Roh H-S, Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and
equilibrium chemical reactions, Energy (2015), http://dx.doi.org/10.1016/j.energy.2015.06.049
19
work transfer, and chemical energy transfer. In thermodynamic
energy transfer, the intensive variable changes such as tempera-
ture, pressure, chemical potential, and electric potential changes
are independent variables in describing the internal convective
processes, and they are not dependent variables described by the
external space and time coordinates. This is the reason why the
expression of the internal energy flux can be written as a product of
temperature, pressure, chemical potential, time, and space
dependent terms when the internal and external phase spaces are
simultaneously considered.
The justification of the postulate for the internal energy flux is
briefly discussed. There are seven fundamental quantities in
physics: distance, time, mass, temperature, electric current,
amount of substance, and intensity of light. From these quantities,
we can say temperature is an independent parameter. Furthermore,
from the amount of substance and electric current, we may analyze
that the particle number and the electric current become inde-
pendent parameters respectively. When we combine the knowl-
edge from thermodynamics with fundamental quantities, we can
confirm that the entropy is an independent parameter as the cor-
responding extensive parameter of the temperature, the chemical
potential is an independent parameter as the corresponding
intensive parameter of the particle number, and the electric po-
tential is an independent parameter as the corresponding intensive
parameter of the electric current. On the other hand, the internal
energy depends on the six parameters of T, S, P, V, m, and N as the
internal degrees of freedom. Since the parameters T, S, m, and N are
independent, we may assume that the parameters P and V are also
independent even though there is no explicit proof. As an implicit
illustration, it may be pointed out that the PeV, TeV, PeT, or
PeTeV property diagrams are frequently utilized to understand
phase transition processes in thermodynamics.
Employing the product form of the internal energy flux u ¼ q(T)
w(P)g(m)B(t)A(r) means the dependence of thermodynamic variable
changes to the internal energy for internal convective mechanisms
[30e36]. In this formalism, the difference between internal
convective mechanisms and external diffusion mechanisms are
clearly clarified. The two distinct mechanisms are separable in
generalized internal and external coordinates. The internal convec-
tive mechanisms of heat transfer, chemical energy transfer, and work
transfer are formulated based on empirical data in which each en-
ergy transfer is a function of its corresponding intensive variable.
Each energy flux is proportional to its intensive variable change:
qT f DT for heat transfer,
wP f DP for work transfer,
gm f Dm for chemical energy transfer.
The energy fluxes are independent of the external space and
time coordinates in these internal convective mechanisms. The
internal degrees of freedom for temperature, pressure, and chem-
ical potential as internal phase spaces do not depend on the
external space and time coordinates. On the other hand, in the
conductive quasi-equilibrium mechanisms, each energy flux is
proportional to its intensive variable gradient:
qdT f VT for heat transfer (heat conduction),
wdP f VP for work transfer (work diffusion),
gdm f Vm for chemical energy transfer (migration).
These energy fluxes in conduction or diffusion mechanisms
explicitly depend on the external space and time coordinates.
As the explicit illustration of the chemical energy transfer the-
ory proposed, the theory can be applied to several chemical re-
actions. It predicts multiple step reaction processes and their
20 H.-S. Roh / Energy xxx (2015) 1e21
Table 6
Comparison among energy transfer processes.
Energy transfer Heat transfer (solidification) Heat transfer (boiling)
Conduction Isothermal Isothermal
Isentropic Isentropic
Internal convection Convection Convection
Nucleation Nucleate
Transient Transition
Film Film
corresponding process times. For example, we can consider the
hydrogeneiodine reaction. During an activation reaction, a bimo-
lecular reaction takes place, and the reaction consists of the mul-
tiple processes. The reaction speed of the first process is slow, and
the Gibbs energy change during the process is small. On the other
hand, the reaction speed of the second process is fast, and the Gibbs
energy change during the process is large. Due to the lack of useful
measurement data for the purpose of the comparison with theo-
retical calculations, only the sketches of theoretical predictions are
presented in the previous subsection. Therefore, more systematic
measurements are demanded to evaluate the predictions.
Two phenomenological diffusion equations are derived from the
chemical energy theory as special cases:
Migration equation,
Concentration diffusion equation.
They are well defined equations and are classified as quasi-
equilibrium processes. Their mechanisms depend on external
space and time coordinates. The chemical energy theory predicts
equilibrium and non-equilibrium processes in addition to them.
These internal processes do not depend on the external space and
time coordinates, but do depend on internal degrees of freedom.
Table 6 explains the non- and quasi-equilibrium energy transfer
processes. The mechanisms of chemical reactions possess similar
characteristics with polarization, solidification, boiling, and liq-
uidevapor phase transition [30e36]. In the kinetics of chemical
reactions, the four control mechanisms of activation, concentration,
transition, and film chemical energy are taken into account, and the
characteristics of the chemical potential, temporal, and spatial
dependence of chemical energy transfer are demonstrated. The
kinetics of electrochemical reactions (polarization) contains the
four control mechanisms of activation, concentration, resistance,
and film polarization. Likewise, solidification, pool boiling, and
liquidevapor phase transition predicts the four control
mechanisms.
In Eq. (21) or Eq. (23), we are interested in the chemical internal
convective effects under the assumption of constant temperature
and constant pressure. However, if the chemical reaction takes
place only under a constant pressure, the differential equation leads
to the enthalpy flux h:
l V$h  [T0 vh/vΤ þ kBT0 vh/vm] þ t vh/vt ¼ 0.
The nonzero a and N lead to the coupled transfer with heat and
chemical energy transfer in a system and the enthalpy change DH is
the relevant thermodynamic potential change. Hence, the above
equation offers the solution for the enthalpy flux (enthalpy per unit
area and unit time):
h (Τ, m, t, r) ¼ q(Τ)g(m)B(t)A(r) ¼ h0 exp (DH/kBT0) exp (bt/t) exp
(k$r/l)
where the temperature dependence reflects an Arrhenius type
equation.
Please cite this article in press as: Roh H-S, Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and
equilibrium chemical reactions, Energy (2015), http://dx.doi.org/10.1016/j.energy.2015.06.049
Work transfer Electrochemical reaction Chemical reaction
Isobaric Diffusion Diffusion
Isochoric Migration Migration
Convection Activation Activation
Turbulence Concentration Concentration
Transition Resistance Transition
Film Film Film
The Higgs mechanism [40] in quantum field theory of physics is
the relativistic extension of the Ginzburg-Landau theory in non-
relativistic thermodynamics. This implies spontaneous symmetry
breaking mechanisms can be described by the Ginzburg-Landau
theory in thermodynamics. In the Ginzburg-Landau theory, the
scalar fields are recognized as the order parameters during phase
transitions. The scalar fields of temperature, pressure, and chemical
potential can be the order parameters which are independent
variables regardless of external space and time coordinates.
Moreover, it may be feasible that thermodynamic energy can be
quantized.
Chemical energy transfer can thus be applicable in multi-
disciplinary areas: For instance, endothermic or exothermic chemi-
cal reactions, biochemical reactions, polarization and electrodepo-
sition, oxidation and reduction processes, connection with
GinzburgeLandau theory, relativistic extension of thermodynamic
energy transfer, and quantization of thermodynamic energy transfer.
12. Conclusions
We propose the chemical energy transfer theory to clarify the
characteristics of chemical energy transfer mechanisms of non-
equilibrium, quasi-equilibrium, and equilibrium at finite tempera-
ture. The statistical, thermodynamic theory is regarded as a special
case of the statistical internal energy kinetics of heat, chemical
energy, and chemical energy transfer. The chemical energy transfer
theory provides the unified mechanisms of internal convective and
external diffusive chemical reactions. It is the non-equilibrium
generalization beyond the quasi-equilibrium chemical reactions
of the constant chemical potential and constant particle number
processes. The theory is capable of exploring both spontaneous and
nonspontaneous chemical reactions or to both dissociation and
synthesis chemical reactions. It is applicable to any chemical re-
actions regardless of their molecularity and order of reaction.
We apply the chemical energy transfer theory to non-
equilibrium chemical reactions and discuss its logical predictions.
The four control mechanisms, three limiting fluxes, and four acti-
vation parameters are adopted as input parameters. The four re-
gimes formed as a function of chemical potential, time, and
distance are suggested analogously to electrochemical reactions:
activation, concentration, transition, and film chemical reaction
regimes. The Gibbs energy fluxes are predicted as a function of
chemical potential, time, and displacement.
The thermodynamic chemical energy transfer theory is indis-
pensable and promising in practical applications in science and
engineering and is capable of being a pioneering fundamental
approach for equilibrium, quasi-equilibrium, and non-equilibrium
chemical reactions. The chemical energy transfer theory will have
widespread applications relevant to electrochemical reactions,
biochemical reactions, and chemical reactions.
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