Energy 89 (2015) 1029e1049

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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:
Received 22 January 2015
Received in revised form
20 May 2015
Accepted 16 June 2015
Available online 10 July 2015

Chemical energy transfer mechanisms at nite temperature are explored by a chemical energy transfer
theory which is capable of investigating various chemical mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium. Gibbs energy uxes are obtained as a function of chemical potential, time, and
displacement. Diffusion, convection, internal convection, and internal equilibrium chemical energy uxes
are demonstrated. The theory reveals that there are chemical energy ux gaps and broken discrete symmetries at the activation chemical potential, time, and displacement. The statistical, thermodynamic theory
is the unication of diffusion and internal convection chemical reactions which reduces to the nonequilibrium generalization beyond the quasi-equilibrium theories of migration and diffusion processes.
The relationship between kinetic theories of chemical and electrochemical reactions is also explored. The
theory is applied to explore non-equilibrium chemical reactions as an illustration. Three variable separation constants indicate particle number constants and play key roles in describing the distinct chemical
reaction mechanisms. The kinetics of chemical energy transfer accounts for the four control mechanisms of
chemical reactions such as activation, concentration, transition, and lm chemical reactions.
2015 Elsevier Ltd. All rights reserved.

Keywords:
Thermodynamic chemical energy transfer
theory
Chemical non-equilibrium
Chemical quasi-equilibrium
Chemical equilibrium
Chemical and electrochemical reactions
Four control mechanisms

1. Introduction
Energy transfer is a central process in the evolution of the universe, and one distinctive form of energy transfer is chemical energy
transfer. Thermodynamics dealing with energy transfer and chemical energy transfer dealing with chemical reactions have various
application areas in science and engineering. The coupled mechanisms of thermodynamic and chemical reactions are denitely
demanded in diverse elds including phase transition, chemistry,
electrochemistry, corrosion, thermal devices, microscopic organisms, physics, mechanical engineering, biology, and energy.
Extensive research has been conducted for developing a thermodynamic theory to describe chemical reaction processes. Existing theories of chemical kinetics include the Arrhenius equation,
collision theory, potential energy surfaces, Gibbs ux formalism,
Lagrangian formalism, and transition state theory [1e26]. Nevertheless, chemical reaction mechanisms are so complicated that
their entire understanding in terms of existing theories [27e29] is

* Tel.: 1 212 650 6759; fax: 1 212 650 8013.

E-mail address: hroh@ccny.cuny.edu.
http://dx.doi.org/10.1016/j.energy.2015.06.049
0360-5442/ 2015 Elsevier Ltd. All rights reserved.

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 concentration equation for mass (or particle number) transfer [33] is
useful in investigating particle diffusion:

vC=vt va $VC D0 V2 C 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 claried so
far. The other existing theories for chemical reactions are established 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 dynamic properties are not given explicitly [10e12,27]. Therefore, a
robust theory of chemical reactions should provide essential dynamic and static information about chemical reactions under a

1030

H.-S. Roh / Energy 89 (2015) 1029e1049

certain fundamental principle. We are here interested in a chemical

energy transfer theory which are simultaneously capable of integrating thermodynamic, spatial, and temporal properties as well as
describing non-equilibrium, quasi-equilibrium, and equilibrium
processes.
An internal energy transfer theory [30] for thermodynamic nonequilibrium, quasi-equilibrium, and equilibrium has been proposed. The systematically unied transport theory is capable of
producing the three energy transfer mechanisms of thermodynamics so that it estimates parameters in thermodynamic equilibrium and non-equilibrium states and claries the characteristics
of transport processes [30e36]. The kinetic theory is also applicable
to understanding the chemical energy transfer mechanisms in
various chemical phenomena in nature.
We have furthermore proposed the statistical thermodynamic
theory for electrochemical reactions [31,32] which is vital to
examine both diffusive and internal convective electrochemical
reactions. It is a transport theory for electrochemical reactions
leading to the integration of diffusion and internal convection, a
generalization beyond quasi-equilibrium theories for migration
and diffusion, and the unication of internal equilibrium and
equilibrium. The Nernst equation is derived from the internal
convective and equilibrium processes, the time rate of electrochemical reactions is obtained, and the spatial cross section is
gained from the kinetic theory.
In these contexts, we propose a chemical energy transfer theory
for non-equilibrium, quasi-equilibrium, and equilibrium chemical
energy as a special case of the internal energy transfer theory [30].
The theory is analogous to the statistical thermodynamic theory for
electrochemical reactions [31,32]. It is able to probe internal
convective chemical energy transfer in chemical reactions since it is
a generalization beyond chemical energy transfer in quasiequilibrium. It is thus a non-equilibrium extension beyond chemical equilibrium and quasi-equilibrium. It is based on the conservation of energy rather than the rate of chemical reactions based on
the conservation of mass which the existing theories [27e29]
depend on. The chemical transfer theory provides the chemical
potential and spatial dependence in addition to the temporal
dependence of chemical reactions. The theory is likewise competent to explore both dissociation and synthesis chemical reactions
regardless of the molecularity of a chemical reaction.
In the chemical energy transfer theory, the Gibbs energy uxes
are described as a function of chemical potential, time, and
displacement simultaneously under a postulate that chemical potential, time, and displacement are independent and orthogonal
variables in extended phase spaces. This is the rst rigorous
microscopic kinetic theory for internal convective chemical energy
transfer.
External convective energy transfer is formulated in addition to
internal convective energy transfer. Moreover, the thermodynamic
behavior of the equilibrium chemical process is claried through
the theory. A connection between a rate equation and a reaction
quotient is also proved through the chemical energy transfer theory
since they are dependent on both concentration and temperature.
Fig. 1 sketches the hierarchy for energy transfer which consists
of heat, work, and chemical energy transfer [30e36]. Each energy
transfer possesses three modes of conduction (or diffusion), convection, and radiation in addition to equilibrium. Aside from radiation, this paper concentrates on internal convection, conduction,
internal equilibrium, and convection of chemical energy transfer to
explore chemical reactions. Moreover, the statistical thermodynamic theory of electrochemical reactions is reviewed as a branch
of the chemical energy transfer.
The objective of this paper is hence to establish a chemical energy transfer theory for chemical reactions and to apply the

Fig. 1. Chemical energy transfer in the hierarchy for energy transfer mechanisms.
Electrochemical energy transfer is considered as a branch of chemical energy transfer.

chemical energy transfer theory to examine various chemical reactions to clarify their features. The theory is utilized to examine
chemical energy transfer mechanisms in equilibrium, quasiequilibrium, and non-equilibrium. The chemical energy transfer
theory can be applied to internal convective chemical processes at a
solideliquid boundary as its demonstration. Chemical energy ux
proles are predicted as a function of chemical potential, time, and
distance. The four control regimes are also anticipated as a function
of chemical potential, time, and distance in analogy with electrochemical reaction regimes: activation, concentration, transition,
and lm chemical reaction regimes.
2. Internal energy transfer theory
The internal energy transfer theory [30] has been proposed for
the transfer mechanisms of heat, work, and chemical energy. A total
system containing reactants and products is thermodynamically
isolated from its surroundings, and has thermodynamic energy
transfer due to thermal, mechanical, and chemical non-equilibrium
between reactants and products. The local thermodynamic nonequilibrium is characterized as the intensive variables of temperature, pressure, and chemical potential [37].
2.1. Motivation of internal energy transfer
Internal energy transfer theory is motivated from the thermodynamic point of view in which internal energy transfer depends
on intensive state variables as well as extensive state variables.
Internal energy transfer in a quasi-equilibrium (quasi-static) process is conventionally described only by extensive state variables,
but internal energy in a non-equilibrium process can be stated by
including intensive state variables. Here, the dependence of
intensive state variables for internal energy transfer is discussed
[30,31,33].
Euler's equation of thermodynamics for the internal energy is
U (T, S, P, V, m, N) TS  PV mN.
From Euler's equation, we have the rst law of thermodynamics:
dU dQ  dW dG.
Rewriting the rst law, we obtain
dU (T, S, P, V, m, N) (TdS  PdV mdN) (SdT  VdP Ndm)
where

dQ (T, S) TdS SdT,

(2)

H.-S. Roh / Energy 89 (2015) 1029e1049

dW (P, V) PdV VdP,

dG (m, N) mdN Ndm.
For a quasi-equilibrium process, the fundamental equation of
thermodynamics is given by
dU (S, V, N) TdS  PdV mdN,

1031

Irreversible non-equilibrium processes take place if T > Ta, P > Pa,

and m > ma while reversible equilibrium processes occur if T < Ta,
P < Pa, and m < ma. Table 1 summarizes non-equilibrium, quasiequilibrium, and equilibrium processes.
Irreversible non-equilibrium processes take place if T > Ta,
P > Pa, and m > ma while reversible equilibrium processes occur if
T < Ta, P < Pa, and m < ma:

where the GibbseDuhem equation is observed:

Internal energy transfer, dU (T, S, P, V, m, N)

(TdS  PdV mdN) (SdT  VdP Ndm),

SdT  VdP Ndm 0.

Heat transfer,

On the other hand, for a non-equilibrium or equilibrium process,

we have

Work transfer,

dQ (S, T) TdS SdT,

dW (V, P) PdV VdP,

Chemical energy transfer,

dU (S, V, N) < TdS  PdV mdN.

dG (N, m) mdN Ndm,

Combining non-equilibrium, quasi-equilibrium, and equilibrium

processes, we can rewrite

Irreversible quasi-equilibrium processes take place if T > Ta,

P > Pa, or m > ma while reversible quasi-equilibrium processes occur
if T < Ta, P < Pa, or m < ma:

dU (S, V, N)  TdS  PdV mdN,

Internal energy process,

(3)

which is the fundamental thermodynamic relation.

Comparing Eq. (2) with Eq. (3), we can analyze that

Isothermal process,
Isobaric process,

SdT  VdP Ndm  0.

(4)

dU (T, P, m) SdT  VdP Ndm 0,

dQ (S) TdS if dT 0,

dW (V) PdV if dP 0,

Constant chemical potential process, dG (N) mdN if dm 0.

From the above equation, we have the conditions of distinct thermodynamic processes:
For a quasi-equilibrium process, it reduces to the GibbseDuhem
equation

Irreversible quasi-equilibrium processes take place if T > Ta,

P > Pa, or m > ma while reversible quasi-equilibrium processes occur
if T < Ta, P < Pa, or m < ma:

SdT  VdP Ndm 0.

Internal energy process,

For a non-equilibrium or equilibrium process, it holds the

inequality condition

Isentropic process,

dQ (T) SdT if dS 0,

Isochoric process,

dW (P) VdP if dV 0,

SdT  VdP Ndm > 0.

Distinction between non-equilibrium and equilibrium depends on
whether temperature, pressure, and chemical potential are larger
than their corresponding activation temperature, activation pressure, and activation chemical potential.
In summary, we analyze that there are two contributions in
internal energy transfer in Eq. (2). The rst 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 specically classify non-equilibrium,
quasi-equilibrium, and equilibrium processes. We utilize the denitions of the thermodynamic potentials:
Gibbs free energy,
Heat potential,
Grand potential,

G U  TS PV mN,

Q U PV  mN TS,
W U  TS  mN 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,

dU (S, V, N) TdS  PdV mdN 0,

Constant particle number process, dG (m) Ndm if dN 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 ux (or internal
energy intensity) can be described as a function of temperature,
pressure, chemical potential, time, and space:
u u (T, P, m, t, r).
It is assumed that the ve variables are independent and orthogonal. Furthermore, the expression of the internal energy ux can be
written as a product of temperature, pressure, chemical potential,
time, and space dependent terms:
u q(T)w(P)g(m)B(t)A(r).
The internal energy ux in thermodynamics under the postulate
is described by a partial differential equation:

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H.-S. Roh / Energy 89 (2015) 1029e1049

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
Thermal energy
(heat)
Mechanical energy
(work)
Internal energy

dG (m) Ndm if dN 0.
dQ (T) SdT if dS 0

dG (N) mdN if dm 0
dQ (S) TdS if dT 0

dG (N, m) mdN Ndm

dQ (S, T) TdS SdT

dW (P) VdP if dV 0,

dW (V) PdV if dP 0

dW (V, P) PdV VdP

dU (S, V, N) TdS  PdV mdN 0

dU (T, P, m) SdT  VdP Ndm 0

dU (T, S, P, V, m, N) (TdS  PdV mdN) (SdT  VdP Ndm)

lV$u t Du/Dt 0

(5)

where u un is the total energy ux vector (or the power density

vector) with the unit vector n. The internal energy ux u is dened
by internal energy per unit area and unit time. t is the total reaction
time which is dened by the mean reaction time t0 multiplied by
the particle number of the system, and l is the total mean free path
which is dened by the mean free path l0 multiplied by the particle
number of the system.
D/Dt represents the thermodynamic convective derivative:
D/Dt v/vt vT$V
v/vt  [T0 v/v (kBT0/ v0) v/vP kBT0 v/vm]/t

(6)

where is the temperature, P is the pressure, and m is the chemical

potential. v0 is the equilibrium volume V0 per particle number, T0 is
the equilibrium temperature, and kB is the Boltzmann constant. In
Eq. (6), we introduce the thermodynamic velocity vector

vg/vm (n/kBT0) g(m) 0,

(11)

vB/vt (b /t) B(t) 0,

(12)

V$ (k/l) (r) 0.

(13)

Eq. (9) represents the heat transfer equation, and Eq. (10) stands for
the work transfer equation. Eq. (11) shows the chemical energy
transfer equation and leads to the Nernst equation. Eq. (12) and (13)
reect the temporal and spatial equations for energy transfer,
respectively.
The ve constants a, z, n, b, and k in the separation of variables
are introduced:

a: thermal particle number constant,

z: mechanical particle number constant,
n: chemical particle number constant,
b: temporal particle number constant,
k: spatial particle number constant.

vT l/t (i j k)
and the thermodynamic derivative vector

The particle number constants in the above are constrained by:

In nonrelativistic case,

V (i T0v/v j P0v/vP k m0v/vm)/l.

a z n d,

The intrinsic intensive property dimensions of temperature, pressure, and chemical potential play the roles of momentum dimensions 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 dimensions in a material space like the conventional space and momentum dimensions.
Eq. (5) can be fully expressed as

d k  b 0.

lV$u  [T0 vu/v (kBT0/v0) vu/vP kBT0 vu/vm] tvu/vt 0. (7)

The rst 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 equation since the thermodynamic intensive variables in Eq. (7) are
included as phase spaces and the internal energy ux in Eq. (7) is
proportional to the phase space distribution in the Liouville equation [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 ux
u (, P, m, t, r) q()w(P)g(m)B(t)A(r),

vw/vP (zv0 /kBT0) w(P) 0,

a2 z2 n2 d2,
d2 k2  b2 0.
The thermal particle number constant in Eq. (9) is connected to
the entropy change by a ln U 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 V0/k. n
in Eq. (11) represents the particle number change in specic particle species. kr b/t 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 (b2  d2)1/2 l/l0 in Eq. (13) is connected to the reaction cross section sc V/kl0 v0/l0.
As for the solutions of internal convection and diffusion energy
uxes (uu and ud) in the non-equilibrium process of nonzero T, P, m,
t, and r, we nd the following integrated solutions from (9)e(13),
respectively:
q(S) q0 exp (aS/T0),

(14)

w(PV) w0 exp (zv0PV/kBT0),

(15)

g(mN) g0 exp (nmN/kBT0),

(16)

B(tB) B0 exp (btB/t),

(17)

(8)

we derive ve differential equations from (7):

vq/v (a/T0) q() 0,

In relativistic case,

(9)
(10)

H.-S. Roh / Energy 89 (2015) 1029e1049

(rB) A0 exp (k$rB/l),

(18)

where k kn (b2  d2)1/2n and n is the unit vector along the diffusion
direction of the energy ux. Eq. (14)e(16) reect 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:

1033

The statistical thermodynamic theory for electrochemical reactions [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 dened by G SmiNi and the Gibbs energy transfer per area per unit
time between reactants and products can be dened by g (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 C,

S jT  T0j,

B C > AB.

PV jP e P0j,

More general chemical reactions take the form

mN jm  m0j,

oO pP > rR sS.

tB jt  t0j,

The Gibbs energy change in a chemical reaction DG is dened by

rB jr  r0jn.

DG G(products)  G (reactants) Gp  Gr.

At large TS, PV, mN, rB, or tB, the corresponding energy ux 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 internal energy ux takes the form

(20)

We adopt a postulate that the Gibbs energy ux can be

described as a function of chemical potential, time, and space:
g g (m, t, r).
Furthermore, the expression of the Gibbs energy ux can be written
as a product of chemical potential, time, and space dependent
terms:

u (S, PV, mN, tB, rB) u0 exp [(akBS zv0PV nmN)/kBT0] exp (btB/t) exp (k$rB/l)
0
u0 exp [(DQS  DWV DGN)/kBT0] exp (btB/t) exp (k$rB/l)
00
u exp (DUB/kBT0) exp (btB/t) exp (k$rB/l)
0

where u0 q0w0g0B0A0.
The heat reaction quotient Zq exp(DQS/kBT0) for a heat
ensemble, the work reaction quotient Zw exp(DWV/kBT0) for a
grand canonical ensemble, and the Gibbs reaction quotient
Zg exp(DGN/kBT0) for a Gibbs ensemble. Hence, we analyze that

DQS (DQ  DQ0) akBS akBjT  T0j,

DWV (DW  DW0) zVPV zv0jP e P0j,
DGN (DG  DG0) nmN njm  m0j,
DUB (DU  DU0) DQS  DWV 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 z 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 mechanical isolation. For the system in chemical non-equilibrium, the
physical mechanisms of energy transfer can be described by
physical parameters in local thermodynamic equilibrium.

(19)

g g(m)B(t)A(r).
To describe chemical reactions, Eq. (7) can be expressed as

l V$g  kBT0 vg/vm t vg/vt 0

(21)

where g gn is the Gibbs energy ux vector with the unit vector n.

The second term represents the internal convective Gibbs energy
transfer in the chemically isolated system under constant temperature 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
satises 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 t vg/vt 0

(22)

where va l/t is the average particle speed and g gd gv is the

Gibbs energy ux of diffusion and convection. Eq. (22) is the
transform of the continuity equation
V$g emvn0/vt 0
where n0 is the particle number density, em is the Gibbs energy
change per particle, and emn0 g/va is the Gibbs energy change per
unit volume.

1034

H.-S. Roh / Energy 89 (2015) 1029e1049

The external Gibbs energy ux in the rst term of Eq. (21) is

comprised of the convection energy ux gv and the diffusion energy
ux gd:
g gd gv.
The internal Gibbs energy ux in the second term of Eq. (21) is
made of the internal convection energy ux gm and the internal
equilibrium energy ux g0:
g gm g0.
Fig. 2 presents the chemical energy transfer theory dealing with
the four regions of non-equilibrium, irreversible quasi-equilibrium,
reversible equilibrium and equilibrium. The theory offers governing
equations for the internal equilibrium, internal convection, external
convection, and conduction mechanisms. Fig. 3 exhibits relationships among these processes. Non-equilibrium reactions contain
internal convection processes, and equilibrium reactions represent
internal equilibrium processes. Quasi-equilibrium reactions of
external convection and diffusion include migration and concentration diffusion processes. Governing equations and solutions in
the four regions are described in the following sections.
Relationships among subjects in the chemical energy transfer
theory of chemical reactions are shown in Fig. 4. The chemical energy
transfer theory renders the reaction quotient, and thermodynamics
denes the reaction quotient. In chemical equilibrium, the equilibrium constant is dened and is estimated by statistical mechanics.
Conventional transport phenomena near equilibrium are connected
to the equations of diffusion and migration. The rate equation known
as the kinetics of chemical reactions is derived as a special case of the
chemical energy transfer theory. Thermodynamics, statistical mechanics, and kinetics viewpoints depend on energy, probability, and
rate considerations, respectively.
4. Chemical energy transfer for non-equilibrium chemical
reactions

where n0 is the particle number density and em is the chemical

energy per particle.
We deal with the diffusion and internal convective effects.
When we use the method of separation of variables for the Gibbs
energy ux
gm(m, t, r) g(m) B(t) A(r),
we derive the following three differential equations from Eq. (23):
vg/vm (n/kBT0) g(m) 0,

(24)

vB/vt (b /t) B(t) 0,

(25)

V$A (k/l) A(r) 0.

(26)

Eq. (24) denotes the chemical energy transfer. Eqs. (25) and (26)
represent the temporal and spatial equations for chemical energy
transfer, respectively.
The three constants n, b, and k in the separation of variables are
introduced, and their constraint is expressed as:
In nonrelativistic case,

n k  b 0.
In relativistic case,

4.1. Non-equilibrium chemical reactions

The governing equation for non-equilibrium chemical reactions
can be expressed as

l V$gm  kBT0 vgm/vm t vgm/vt 0.

Fig. 3. Hierarchy in chemical reactions.

(23)

The above equation is the extension of the continuity equation for

diffusion:
V$gd em vn0/vt 0

Fig. 2. Four chemical energy transfer regions of non-equilibrium, irreversible quasiequilibrium, reversible quasi-equilibrium and equilibrium.

n2 k2  b2 0.
The relativistic constraint is applied to classify different processes
even though nonrelativistic governing equations are addressed.
he separation constants indicate.

n: chemical particle number constant,

b: temporal particle number constant,
k: spatial particle number constant.

Fig. 4. Relationships among subjects in the chemical energy transfer theory of

chemical reactions.

H.-S. Roh / Energy 89 (2015) 1029e1049

Eq. (25) represents the rate equation in chemical reactions.

kr b/t 1/t0 in Eq. (25) stands for the rate constant in chemical
reactions and is the inverse of the mean reaction time t0.
k (b2  n2)1/2 l/l0 in Eq. (26) is connected to the reaction cross
section sc V/kl0, and n0 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 chemical energy ux (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) g0 exp (nmN/kBT0),

(27)

B(tB) B0 exp (btB/t),

(28)

A(rB) A0 exp (k$rB/l),

(29)

2 1/2

where k kn (b  n ) n and n is the unit vector in the

diffusion direction of the Gibbs energy ux.
Eqs. (27)e(29) satisfy the initial and boundary conditions. The
chemical potential, time, and displacement variables are represented as the excess quantities, respectively:

mN jm  m0j,

1035

Zg 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 0
represents the chemical energy transfer process due to the diffusion 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 number constant b gives the information of process speed. From Eq.
(28), the behavior of time is obtained:
t t0  (t /b) ln M t0  t0 ln M
where M B/B0 gt/g0t with the exchange chemical energy ux 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 b/t 1/t0, Eq. (28) is analogous to the rate
law of the rst order or the pseudo-rst order chemical reaction
under the assumption that the quantity B is proportional to the
concentration:
vB/vt kr B(t) 0.

tB t  t0,
rB jr  r0jn.

(30)

At large mN, rB, or tB, the corresponding chemical energy ux

amplitude converges to zero.
The chemical energy density is thus of the nal form:
0

gm(mN, tB, rB) g0 exp (nmN/kBT0) exp (btB/t) exp (k$rB/l) (31)
00

00

where g g0 B0 A0. The normalization condition for g may yield

00

g n0 (ek Pv0) va (k/V)emva

sc 1/n0l0.
From Eq. (29), the spatial coordinate is given by
r r0  n(l/k) ln L (r0  l0 ln L)n

where va (8kBT0/m0p)1/2 is the mean speed in thermal

equilibrium.
Eq. (27) can be utilized to understand the Gibbs energy ux 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 dened by

DGN DG  DG0 nmN njm  m0j,

DG DG0 kBT0 ln Zg,
Zg exp (DGN/kBT0),

m m0  (kBT0/n) ln Zg.

Eq. (29) leads to the spatial dependence of the convection energy 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 V/kl0:

(32)

These equations may be useful to explore the chemical energy

transfer. In chemical reactions,
K 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:

where L A/A0 gr/g0r with the exchange chemical energy ux 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 quasiequilibrium, 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 classies thermodynamic, spatial, and temporal
energy transfer mechanisms in equilibrium, reversible quasiequilibrium, 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 mechanisms. 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 0
(nonzero n, mN and b; k 0).
Non-uniform and steady chemical reactions with n2 k2 0
(nonzero n, mN, and k; b 0).

1036

H.-S. Roh / Energy 89 (2015) 1029e1049

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

Equilibrium
Reversible quasi-equilibrium
Irreversible quasi-equilibrium
Non-equilibrium
Equilibrium
Reversible quasi-equilibrium

Internal energy

Irreversible Quasi-equilibrium
Non-equilibrium

Thermodynamics

Space

Time

m 0 for njm  m0j

n 0, m0 s 0
m0 0, n s 0
n 0, mN s 0
mN 0, n s 0
nmN njm  m0j s 0
T P m 0 for akBSzv0PV nmN
a z n 0 nonzero 0,P0,m0
0 P0 m0 0
a z n 0 nonzero S, PV, mN
S PV mN 0
akBS zv0PV nmN s 0

r 0 for k$jr  r0jn

k 0, r0 s 0
r0 0, k s 0
k 0, rB s 0
rB 0, k s 0
k$rB k$jr  r0jn s 0
r 0 for k$jr  r0jn
k 0, r0 s 0
r0 0, k s 0
k 0, rB s 0
rB 0, k s 0
k$rB k$jr  r0jn s 0

t 0 for bjt  t0j

b 0, t0 s 0
t0 0, b s 0
b 0, tB s 0
tB 0, b s 0
btB bjt  t0j s 0
t 0 for bjt  t0j
b 0, t0 s 0
t0 0, b s 0
b 0, tB s 0
tB 0, b s 0
btB bjt  t0j s 0

Table 3
Spontaneity conditions for chemical energy transfer mechanisms.
Energy transfer
Chemical energy

Internal energy

Spontaneous
Equilibrium
Non-spontaneous
Spontaneous
Equilibrium
Non-spontaneous

The governing equation for steady and uniform chemical energy

transfer leads to
kBT0 vgm/vm  t vgm/vt 0.

(33)

Thermodynamics

Space

Time

n>0
n0
n<0
d>0
aznd0
d<0

k
k
k
k
k
k

>0
0
<0
>0
0
<0

b>0
b0
b<0
b>0
b0
b<0

where m is the chemical potential and C is the particle number

density. In non-equilibrium, the differential Eq. (35) leads to two
equations for the intensive and the extensive variable under the
assumption that m and C are orthogonal and independent:

l V$C  kBT0 vC/vm t vC/vt 0,

The chemical energy density takes the integrated solution:

0

gm(mN, tB) g0 exp (nmN/kBT0) exp (btB/t)

l V$m  kBT0 t vm/vt 0.

00

where g g0B0 and b2 n2.

Non-uniform and steady chemical energy transfer is given by
the partial differential equation:

V$jdd  (kBT0/t)vC/vm vC/vt 0,

l V$gm  kBT0 vgm/vm 0.

V$jdm  (kBT0/t) vm/vt 0,

(34)

The chemical energy density is thus of the nal form:

where Fick's rst law jdd Cva D0VC and the migration current
density jdm mva DmVm are utilized under the assumption of
constant temperature and constant pressure. The rst is the concentration diffusion equation for an isotropic process, and the
second is the migration equation for an isotropic process:

gm(mN, rB) g0 exp (nmN/kBT0) exp (k$rB/l)

0

where g0 g0A0 and k2 n2.

5. Chemical energy transfer for irreversible quasiequilibrium chemical reactions
The internal source Ci in Eq. (1) can be identied from Eq. (23).
Eq. (23) can be written as

m[l V$C  kBT0 vC/vm t vC/vt] C[l V$m  kBT0 t vm/vt]

0

Rewriting the above equations, we nd

(35)

D0V2C  vC/vt (kBT0/t)vC/vm,

(36)

DmV2m  vm/vt kBT0/t,

(37)

where D0 val0/3 is the concentration diffusion coefcient and

Dm val0/3 l20/3t0 is the migration coefcient. Ci (kBT0/t) vC/vm
is obtained by comparing Eq. (1) with Eq. (36). This means chemical
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
(convection)

Irreversible quasi-equilibrium
(diffusion)

Chemical energy

Chemical potential
(Migration)
Particle number
(Diffusion)

n0
m0 s 0
ns0
m0 0

n0
mN s 0
ns0
mN 0

H.-S. Roh / Energy 89 (2015) 1029e1049

1037

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

Process Variable

Reversible equilibrium
and quasi-equilibrium

Irreversible non-equilibrium
and quasi-equilibrium

Chemical energy

Chemical potential
Particle number

Conservation
Conservation

Decrease
Increase

diffusion equation. The condition for the particle number constants

in Eq. (36) leads to b2 n2 k2.
During quasi-equilibrium chemical reactions, two irreversible
processes are possible:
Migration with b2 n2 k2 (nonzero b and k; n 0),
Concentration diffusion with b2 k2 (nonzero b and k; mN 0).
Quasi-equilibrium transport theories for conduction chemical
reactions are considered as special cases of general chemical reactions (1). Migration and diffusion equations are derived. The
governing equation for diffusion and migration is found to be

l V$gd t vgd/vt 0.

(38)

The zero n process in Eq. (37) represents the chemical energy

migration at constant particle number. The migration equation
becomes
DmV2m  vm/vt 0.

(40)

The constraint for the particle number constants is b2 k2.

m0 jm0  mr0j jm  m0j,

p

t0 t0  tr0 t  t0,
p

r0 jr0  rr0jn jr  r0jn.

Under the parameterization, the governing equation for equilibrium chemical reactions becomes
(41)

When the method of separation of variables for the Gibbs energy

ux

is used, three differential equations are obtained from (41):

(43)

V$A0  k A0 (r) 0.

(44)

The three constants n, b, and k in the separation of variables are

linked to

n2 k2  b2 0.
Eqs. (42)e(44) then yield the following integrated solutions
respectively:
g0 (m0) g0 exp (nm0/kBT0),

(45)

B0 (t0) B0 exp (bt0/t),

(46)

A0 (r0) A0 exp (k$r0/l),

(47)

where k kn (b2  n2)1/2n and n is the unit vector in the

diffusion direction of the Gibbs energy ux.
Eqs. (45)e(47) satisfy the initial and boundary conditions. Note
that Eqs. (27)e(29) lead to Eqs. (45)e(47) at T t r 0,
respectively. The chemical energy density is thus of the nal form:
0

Chemical energy transfer for equilibrium is the reversible process of (nonzero n, b, and k; m t r 0). The equilibrium process
takes place at a nonzero m0 jmp0  mr0j while the chemical potentials
between reactants and products are the same, mp mr; m 0 in (30).
Note that m0 is a variable depending on the chemical potential
difference between mp0 and mr0 while m0 is the equilibrium chemical
potential. Similarly, the spatial and temporal equilibriums are
attained at t r 0 in (30), but t0 and r0 are nonzero variables.
The equilibrium chemical potential, time, and displacement
variables are parameterized as the excess quantities, respectively:

g0(m, t, r) g0(m) B0(t) A0(r)

vB0/vt  (b/t) B0 (t) 0,

g0(m0, t0, r0) g0 exp (nm0/kBT0) exp (bt0/t) exp (k$r0/l)

6. Chemical energy transfer for equilibrium chemical

reactions

l V$g0  kBT0 vg0/vm t vg0/vt 0.

(42)

(39)

The requirement for the particle number constants is b2 k2.

The process of mN jmm0j 0 in Eq. (36) is the particle diffusion
at constant chemical potential. Eq. (36) leads to Fick's second law:
D0V2C  vC/vt 0.

vg0/vm  (n/kBT0) g0 (m) 0,

(48)

where g0 g0 B0 A0.
The activation chemical potential ma, the activation time ta, and
the activation displacement ra are used in the above:
p

ma jm0  mr0jmax jm  m0jmax,

p

ta jt0  tr0jmax jt  t0jmax,

p

ra jr0  rr0jmax jr  r0jmax.

(49)

The integrated solutions of (45)e(47) satisfy g0(m0 0) g0,

B0(t0 0) B0, and A0(r0 0) A0 at the boundary and initial
conditions of m0 0, t0 0, and r0 0, which stand for chemical,
temporal, and spatial equilibriums. Moreover, they satisfy
g0(m0 ma) g1, B0(t0 ta) B1, and A0(r0 ra) A1 at the limiting
conditions of m0 ma, t0 ta, and r0 ra. A variable with the
subscript a denotes the threshold value, and an amplitude variable
with the superscript 1 indicates its limiting value. Using the initial
and limiting conditions, we can evaluate the particle number
constants:

n (kBT0/ma) ln (g1/g0),
b (t/ta) ln (B1/B0),
k (l/ra) ln (A1/A0).
The Gibbs equilibrium constant has the relation
Z0g exp (DG0/kBT0),

1038

H.-S. Roh / Energy 89 (2015) 1029e1049

and the equilibrium constant K0 takes the form

DG/tA zeFE/tA jE with the electric potential E. The relation

between the Gibbs potential and the chemical potential is DG/
N Dm where the other relations are Dm zeFE and N jV/zeFv

K0 exp (DG0/RT0)

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 ux as a function of chemical potential.
The partial differential equation for chemical reaction (23) leads
to a partial differential equation:

exp (nm0/RT0)
exp (njm  m0j/RT0).
Rewriting the above equation, we get the chemical potential during
equilibrium chemical reactions:

m m0 (RT0/n) ln K0.

(50)

7. Chemical energy transfer for reversible quasi-equilibrium

chemical reactions

lV$gE  (RT0/F) vgE/v t dgE/dt 0

(54)

where gE jEE gn is the Gibbs energy ux vector with the unit

vector n. The Gibbs energy ux is dened as the Gibbs energy
change per unit area and unit time.
Eq. (54) reduces to
E[l V$jE  (RT0/F) vjE/v t djE/dt] j[l V$E  RT0/F t dE/dt] 0.

Chemical energy transfer for reversible quasi-equilibrium is the

convection process of (nonzero b and k; n t r 0 or
mN t r 0). The spatial and temporal equilibriums are attained
at t r 0 in (30). The governing equation becomes

Under the assumption that the current density and the electric
potential are orthogonal and independent, we obtain two equations from the above equation:

lV$gv t vgv/vt 0.

l V$jE  (RT0/F) vjE/v t djE/dt 0,

(55)

The particle number constants have a relation:

V$jdm  RT0/Ft dE/dt 0,

(56)

k2  b2 0.

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:

(51)

The equilibrium Gibbs energy ux thus has the nal form:

0

gv (t, r) g0 exp (bt0/t) exp (k$r0/l)

0

where g0 B0 A0.
Eq. (51) leads to the chemical potential conservation (nonzero b
and k; mN t r 0) and particle number conservation (nonzero b
and k; n t r 0):
vm/vt V$(mva) 0,
vC/vt V$(Cva) 0.

(52)

In the presence of convection and diffusion process, the concentration diffusion-convection equation and the migrationconvection equation are given by
V2C  (1/D0) vC/vt  (1/D0) va$VC 0,
V2m  (1/Dm) vm/vt  (1/Dm) va$Vm 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 thermodynamic 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 properties are described. The relation between the current density j and
the Gibbs energy transfer per unit area and unit time is given by

V$jdd (1/v) vjdd/vt 0

(57)

where va 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 q vne/vt 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 reects the internal convective
electrochemical mechanism and is useful to demonstrate polarization 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 electrochemical reaction (55). Using the method of separation of variables
for the current density
jE (E, t, r) j() B(t) A(r),
we derive the following three differential equations from Eq. (55):
vj/vE (zeF/RT0) j() 0,

(58)

vB/vt (b /t) B(t) 0,

(59)

V$A k A(r) 0.

(60)

H.-S. Roh / Energy 89 (2015) 1029e1049

The three constants ze, b, and k in the separation of variables are

introduced, and their relation is given by

1039

l V$jE  (RT0/F) vjE/v 0.

(67)

The current density then takes the form:

z2e k2  b2 0

jE (EP, rB) j0 exp (zeFEP/RT0) exp (k$rB/l)

where the constants denote:

where j0 j0A0 and k2 z2e .

ze: the electrochemical particle number constant,
b: the temporal particle number constant,
k: the spatial particle number constant.

8.2. Irreversible quasi-equilibrium electrochemical reactions: the

processes of (zero ze or zero EP)

ze nNa in Eq. (58) is the charge particle number constant and n is

the mole number of the charge particles. kr b/t 1/t0 in Eq. (59)
stands for the rate constant in electrochemical reactions and is the
inverse of the mean reaction time t0. k (b2  z2e )1/2 l/l0 in Eq.
(60) is connected to the reaction cross section sc V/kl0, and
n0 k/V is the particle number per unit volume.
Then the three integrated solutions for (58), (59), and (60) are
obtained respectively:
P

j( ) j exp (zeFE /RT0),

B

(61)

B(t ) B exp (bt /t),

(62)

A(rB) A0 exp (k$rB/l),

(63)

where k kn (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
Arrhenius type equation.
Eqs. (61)e(63) describe the electric potential dependence,
temporal dependence, and spatial dependence of the current
density, respectively. When the initial and boundary conditions are
applied, the excess forms of the electric potential, time, and
displacement variables relative to their relative equilibriums are
utilized in Eqs. (61)e(63), respectively:
P

E jEeE j,
tB t  t0,
rB jr  r0jn.

During irreversible quasi-equilibrium electrochemical reactions,

two processes are possible to occur:
Migration with b2 k2 (nonzero b and k; ze 0),
Concentration diffusion with b2 z2e k2 (nonzero b and k;
EP 0).
In quasi-equilibrium process, the governing equation becomes

l V$gd t vgd/vt 0.
In the absence of the internal convection source (zero ze), the
governing process is migration with constant particle number. The
homogeneous migration equation for an isotropic process reduces
to
DEV2E  vE/vt 0

(68)

where DE 1/m0s is the migration coefcient and s neq2t0/m is

the electric conductivity. The condition for the constants is b2 k2.
In the absence of the internal convection source (zero
EP jE  E0j), the governing process is the concentration diffusion
with constant electric potential. The homogeneous diffusion
equation for an isotropic process becomes
D0V2 C  vC/vt 0.

(69)

The relation for the constants is b2 k2.

(64)
8.3. Equilibrium electrochemical reactions: the process of (nonzero
ze, b, and k; E 0)

The current density is then found to be the form:

0

jE (EP, tB, rB) j0 exp (zeFEP/RT0) exp (btB/t) exp (k$rB/l) (65)
0

where j0 j0B0A0.
In non-equilibrium electrochemical reactions for nonzero ze, the
Gibbs energy change is not zero: nonzero DG. Two special processes
are possible:
Unsteady and uniform electrochemical reactions with
z2e  b2 0 (nonzero ze, EP and b; k 0),
Non-uniform and steady electrochemical reactions with
z2e k2 0 (nonzero ze, EP, and k; b 0).
The governing equation for unsteady and uniform electrochemical reactions is found to be
(RT0/F) vjE/v  t vjE/vt 0.

(66)

The current density then reduces to the form:

0

jE (EP, tB) j0 exp (zeFEP/RT0) exp (btB/t)

0

where j0 j0 B0 and b2 z2e .

In this case of non-uniform and steady electrochemical reactions, the governing equation becomes

The equilibrium process takes place at a nonzero E0 jEp0  Er0j;

E 0 in Eq. (64). Note that E0 is a variable depending on the electric
potential difference between Ep0 and Er0 while E0 is the equilibrium
potential. Similarly, the spatial and temporal equilibriums are
attained at t r 0 in (64), but t0 and r0 are nonzero variables.
The equilibrium variables are the relative electric potential,
time, and displacement and can be parameterized as
E0 jEp0  Er0j jEeE0j,
t0 tp0  tr0 t  t0,
r0 jrp0  rr0jn jr  r0jn.
Under the parameterization, the governing equation for equilibrium electrochemical reactions leads to

lV$j0  (RT0/F) vj0/v t vj0/vt 0.

(70)

Using the method of separation of variables, we nd governing

equations from (70):
vj0/v  (zeF/RT0) j0 () 0,

(71)

1040

H.-S. Roh / Energy 89 (2015) 1029e1049

vB0/vt  (b/t) B0 (t) 0,

(72)

lV$jv t vjv/vt 0.

V$A0  k A0 (r) 0,

(73)

The particle number constants have a relation:

where the separation variable constants have the relation:

k2  b2 0.

z2e k2  b2 0.

The current density is thus of the nal form:

Applying initial and boundary conditions, we obtain the equilibrium convection current densities from (71)e(73):

jv (t0, r0) j0 exp (bt0/t) exp (k$r0/l)

j( ) j exp (zeFE /RT0),

(74)

B(t0) B0 exp (bt0/t),

(75)

A(r0) A0 exp (k$r0/l).

(76)

(77)

where j0 j0 B0 A0.
The activation potential Ea, activation time ta, and activation
displacement ra are respectively dened by the maximum values in
magnitude:
Ea jEp0 e Er0jmax jE e E0jmax,
ta jtp0 e tr0jmax jt e t0jmax,
ra njrp0 e rr0jmax njr e r0jmax.

(78)

The integrated solutions of (74)e(76) satisfy j0(0 0) j0,

B0(t0 0) B0, and A0(r0 0) A0 at the initial conditions of
E0 0, t0 0, and r0 0, which stand for electrochemical, temporal, and spatial equilibriums. Furthermore, they satisfy
j0(0 a) j1, B0(t0 ta) B1, and A0(r0 ra) A1 at the limiting
conditions of E0 a, t0 ta, and r0 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 (RT0/FEa) ln (j1/j0),

where j0 B0 A0.
Eq. (80) leads to the particle number conservation (nonzero b
and k; ze t r 0):

This reduces to the conservation of convective electric charge or the

conservation of convective mass (the continuity equation):
V$jv q vne/vt 0
where jv qneva. The conservation of electric potential is given by
vE/vt va$VE 0.

9. Chemical reactions and electrochemical reactions

The chemical energy transfer theory of chemical reactions
provides accurate information about the chemical potential,
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 (bk/va) exp(Q/RT0) kr0 exp (Q/RT0)

b (t/ta) ln (B1/B0),
k (l/ra) ln (A1/A0).
From (74), the electric potential becomes
E E0 (kBT0/zeq) ln Z0g
which produces the Nernst equation in an equilibrium electrochemical reaction:
E E0 (RT0/nF) ln K0.

vC/vt V$(Cva) 0.

Eqs. (74)e(76) satisfy the initial and boundary conditions. Note

that Eqs. (61)e(63) lead to Eqs. (74)e(76) at E t r 0,
respectively. The current density then reduces to the nal form:
j0 (E0, t0, r0) j0 exp (zeFE0/RT0) exp (bt0/t) exp (k$r0/l)

(80)

(79)

where kr0 bk/va is the frequency factor which depends on the

reaction
frequency
and
steric
factor,
Q nmaNA nNAjmp0  mr0jmax is the activation energy, and
exp(Q/RT0) reects the fraction of collision with sufcient energy
to produce a chemical reaction.
Fig. 5(a) and Fig. 5(b) respectively show the Gibbs energy ux
and the current density proles during equilibrium processes. The
Gibbs energy ux and the electric current density are respectively
g0(m0) g0 exp (nm0/kBT0),
j0(0) j0 exp (zeFE0/RT0).

8.4. Reversible quasi-equilibrium electrochemical reactions: the

process of (nonzero b and k; ze E 0)
Reversible quasi-equilibriums are the convection electrochemical reactions of (nonzero b and k; ze t r 0 or
EP t r 0). The spatial and temporal equilibriums are attained
at t r 0 in (64), but t0 and r0 are nonzero variables. The governing equation becomes

The Gibbs energy ux at the global equilibrium chemical m0

leads to the exchange chemical energy ux, and the current density
at the equilibrium electric potential E0 reduces to the exchange
current density: g0(m0) g0 and j0(0) j0. The limiting Gibbs
energy ux at the equilibrium process
g1(ma) g0 exp (nma/kBT0)

H.-S. Roh / Energy 89 (2015) 1029e1049

Fig. 5. Gibbs energy ux and current density. The activation chemical potential and
electric potential are measured from their global equilibriums of m0 and E0, respectively. (a) Gibbs energy ux prole as a function of chemical potential during an
equilibrium process. The equilibrium process occurs in the regime of 0 < m0 < ma or
m0 < m < (m0ma). (b) Current density prole as a function of electric potential during an
equilibrium process. The equilibrium process occurs in the regime of 0 < E0 < Ea or
E0 < E < (E0Ea).

is attained at the activation chemical potential ma which is the

maximum chemical potential of m0 jmp0  mr0j jm  m0j. The
activation chemical potential is associated with the work function
difference between reactants and products. It is connected to the
1 0
equilibrium constant Z01
g g /g :

1041

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

displacement. Fig. 6(a) and (b) respectively represent the chemical
energy ux and current density proles in convection mechanisms
until the reversible convection processes reach the initiation displacements of the irreversible quasi-equilibrium migration processes. The spatial chemical energy ux 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 regions 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 convection, and external diffusion. Internal convection is the irreversible non-equilibrium process, and external convection is the
reversible quasi-equilibrium process. Therefore, the chemical energy transfer theory presents the Gibbs energy uxes produced by
the internal equilibrium and internal convective chemical reactions
as well as external convective and external diffusion chemical reactions. 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 displacement ra,
Time reversal symmetry breaking at the activation time ta.
Discrete symmetries are broken, and certain preferred directions are chosen during the irreversible chemical processes. At
the activation chemical potential, the reversible equilibrium process is changed to the irreversible non-equilibrium process. The

ma (kBT0/n) ln Z01
g .
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 ux gap between the limiting energy ux g1 at
the chemical valence band and the exchange energy ux 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 ux 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 activation chemical potential, the equilibrium process reaches the
limiting Gibbs energy ux g1 as shown in Fig. 5(a). The chemical
energy ux gap and the chemical energy gap between the equilibrium and non-equilibrium processes at the activation potential
ma are dependent on the particle number constant n:
Gibbs energy ux gap: Dg g1 e g0,
Gibbs energy gap: DG nma.
Phase transitions caused by chemical energy transfer present
rst order phase transitions since they are accompanied by
discontinuous particle number gaps at activation chemical potentials. 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 ux and current density in the regime of 0 < r0 < ra or
r0 < r < (r0ra). The activation displacement is measured from its global equilibrium
r0. (a) Gibbs energy ux prole as a function of displacement during a convection
process. (b) Current density prole as a function of displacement during a convection
process.

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H.-S. Roh / Energy 89 (2015) 1029e1049

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 ux exponential functions at their corresponding activation
values.
From Table 5, we analyze that the intensive and extensive variables of chemical potential and particle number are conserved
properties during the processes of internal equilibrium and convection. 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 principle. 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 ux proles of internal equilibrium 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 internal 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 proles of internal equilibrium and external convection as a
function of electric potential and space in electrochemical reactions, 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 ux proles of internal
convective and external diffusive mechanisms as shown in Fig. 8.
Fig. 8(a) represents the Gibbs energy uxes of chemical reactions as
a function of chemical potential and space. Fig. 8(b) reects the
current densities of electrochemical reactions as a function of

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
reect 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 electrochemical 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 requirement (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 number constant n represents the chemical energy transfer between the
thermodynamic spaces and the conventional space and time.
The chemical energy uxes in chemical energy transfer are
categorized into six modes:

Fig. 7. Energy ux proles of internal equilibrium and external convection reactions.

(a) Gibbs energy uxes 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.

Fig. 8. Energy ux proles in internal convection and external diffusion energy

transfer mechanisms. (a) Gibbs energy uxes 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.

g gdd gdm gv gm g0 gr
where gdd is the diffusion chemical energy ux due to the concentration gradient VC,
gdm is the migration chemical energy ux due to the chemical
potential gradient Vm,

H.-S. Roh / Energy 89 (2015) 1029e1049

1043

MaxwelleBoltzmann distribution: Zg Pi zNa

gi /Ni!,
BoseeEinstein distribution: Zg Pi zNa
gi ,
FermieDirac distribution: Zg Pi zNa
gi ,
where the reaction activation satises the required rule for individual particle distribution. If the de Broglie wavelength

lT (h2f /2pmkBT0)1/2
Fig. 9. Energy diffusion processes in the absence of internal convection. (a) Chemical
reactions. (b) Electrochemical reactions.

gv is the convective chemical energy ux,

gm is the internal convective chemical energy ux due to the
chemical potential change Dm,
g0 is the internal equilibrium chemical energy ux due to the
equilibrium change m0,
and gr is the radiant chemical energy ux.
The internal convective chemical energy ux gm is generated in the
internal phase space of chemical potential while the diffusion energy uxes are created by the conductive diffusion and migration
processes. The two diffusive chemical energy uxes of migration
and diffusion chemical energy are coupled more or less in phase
transitions. The diffusive chemical energy uxes do not contribute
to the chemical energy ux prole as a function of chemical potential even though they are closely related to the activation
chemical potentials of chemical energy uxes.
The Gibbs reaction quotient Zg can be dened by an extension of
the Gibbs free energy G in analogy to the Gibbs partition function
Z0 kBT0 ln G0 in statistical mechanics:

is small compared with the interparticle wave length, particles in

the system obey MaxwelleBoltzmann statistics. Otherwise, BoseEinstein statistics or FermieDirac statistics is more appropriate.
Equilibrium chemical energy transfer and electrochemical energy transfer are represented as two Eqs. (50) and (79), respectively.

m m0  (RT0/n) ln K0,
E E0  (RT0/zeF) ln K0.
In non-equilibrium, the two intensive variables play essential roles
in chemical reactions and electrochemical reactions.

m m0  (kBT0/n) ln Zg,
E E0  (kBT0/zeF) ln Zg.
The two equations lead to the same form
G G0 kBT0 ln Zg
since Zg KNa. The relative time and displacement are similarly
expressed as
t t0  (t/b) ln Ztg,

Zg exp (DG /kBT0).

At equilibrium, an equilibrium Gibbs transfer function is also
dened:

r r0  n(l/k) ln Zrg,
where Ztg gt/g0t and Zrg gr/g0r.

Z0g exp (DG0/kBT0).

Using the above two equations, we have the actual Gibbs energy
transfer and the equilibrium Gibbs energy transfer:

DG DG0 kBT0 ln Zg kBT0 ln (Zg/Z0g),

DG0 G0p  G0r kBT0 ln Z0g 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 kBT0lnZ0p and G0r kBT0 lnZ0r are the equilibrium
Gibbs free energies for products and reactants, respectively, and Z0p
and Z0r are the conventional Gibbs partition functions of products
and reactants, respectively. The Gibbs reaction quotient can be
connected to the reaction quotient in chemical reactions: Zg KNa.
The conventional Gibbs partition function in statistical mechanics
can thus be related to the activity:

H2 I2 > 2HI,

Z0p (a0p)Na

2NO O2 > 2NO2,

where a0p denotes the equilibrium activity of products.

The Gibbs reaction quotient can also be expressed for subsystems with i species. In this case, we introduce the Gibbs reaction
activation zgi for a particle with species i. Then the reaction quotients for different statistical distributions reduce to:

C2H6 > C2H4 H2.

H2 Br2 > 2HBr,

H2 Cl2 > 2HCl,
2H2 O2 > 2H2O,

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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H.-S. Roh / Energy 89 (2015) 1029e1049

DG0 (Gp0 e Gr0) between chemical reactants and products. Note

that the limiting Gibbs energy ux g1 is identical with the external
Gibbs energy ux ge in Eq. (81).
We dene the activation chemical potential ma, the activation
time ta, and the activation distance ra, respectively, as the
maximum values in their magnitudes:
p

ma jm0 e mr0jmax jm e m0jmax,

p

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 ux in chemical reactions takes

the following form from Eq. (24):
ge g (kBT0/n)dg/dm.

(81)

In the cylindrical coordinates of r, f, and z, as shown in Fig. 10(b),

the chemical energy ux 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 ux
or chemical potential which changes the Gibbs energies in reaction
coordinates.
Fig. 11 shows the Gibbs energy ux proles as a function of
chemical potential during equilibrium and non-equilibrium processes in the presence of external chemical potential. The reversible
and irreversible Gibbs energy uxes respectively take the forms:
g0(m0) g0 exp (nm0/kBT0),
N

g(m ) g [1  exp (nm /kBT0)].

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 ux g0. At the activation chemical potential ma, the equilibrium process gains the limiting Gibbs energy
ux g1 as shown in Fig. 11. The chemical energy ux gap between
the equilibrium and non-equilibrium processes depends on the
particle number constant n. Above the activation chemical potential, a non-equilibrium process proceeds from the exchange Gibbs
energy ux g0 toward the limiting Gibbs energy ux g1. The nonequilibrium process is an irreversible process, and the limiting
Gibbs energy ux in equilibrium plays the role of an internal Gibbs
energy ux so that the non-equilibrium process eventually rises to
the limiting Gibbs energy ux as the excess chemical potential
increases. The limiting Gibbs energy ux g1 is determined by the
equilibrium process caused by the Gibbs energy difference

Fig. 11. Gibbs energy ux proles as a function of chemical potential during the
equilibrium process of m0 < m < (m0 ma) and the non-equilibrium process of
m > (m0 ma) in the presence of external chemical potential. The activation chemical
potential is measured from its global equilibrium m0.

ta jt0 e tr0jmax jt e t0jmax,

p

ra jr0 e rr0jmax jr e r0jmax.

The particle number constants are found to be

n (kBT0/ma) ln (g1/g0),
b (t/ta) ln (B1/B0),
k (l/ra) ln (A1/A0),
where g0 is the exchange Gibbs energy ux and g1 is the limiting
Gibbs energy ux.
The relativistic relation among the particle number constants is
determined by

n2 k2  b2 0.
When we apply the restriction to chemical reactions, we classify the
following three non-equilibrium regimes:

n2 b2 > 0 and k2 0 for activation reactions,

n2 b2  k2 > 0 for concentration reactions,
n2 b2  k2 < 0 for transition reactions.
Moreover, the process conversion from non-equilibrium to equilibrium takes place in transition reactions:

n2 b2  k2 > 0 for transition reactions,

n2 b2  k2 < 0 for lm 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 lm reactions. The four regimes are analogous to the
four regimes designed in the polarization processes of electrochemical 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 uxes in concentration and transition
chemical energy transfer. The chemical energy ux by reactants is
larger than the chemical energy ux by products in concentration
chemical energy transfer while the chemical energy ux by products is larger than the reactant chemical energy ux in transition
chemical energy transfer. In concentration chemical energy transfer, the chemical energy ux by reactants governs while in lm
chemical energy transfer, the chemical energy ux by products

H.-S. Roh / Energy 89 (2015) 1029e1049

g g1A [1  exp (namA/kBT0)] g1C [1  exp (ncmC/kBT0)]

[g1C exp (nat mT/kBT0) H(mtr  m) g1Fexp (nbt mF/kBT0)
H(mtr  m)] g1F exp (nfmF/kBT0)

1045

(86)

where H is the Heaviside step function. The transition chemical

potential is expressed as

mtr [1/(nbt  nat )] [(nbt maf  nbt mat) ln(g1C/g1F)].

Fig. 12. Four control regimes formed by reaction processes. (a) Chemical reactions. (b)
Polarization in electrochemical reactions.

governs. There are a maximum limiting energy ux in the convection mechanism, a maximum energy ux in the concentration
mechanism, two maximum and minimum limiting chemical uxes
in the transition mechanism, and a minimum limiting energy ux
in the lm mechanism.
We here concentrate on the application of Eq. (81) to nonequilibrium chemical reactions. As Fig. 12 shows, the probable
behavior of chemical energy ux in the nonzero modes of n in a nonequilibrium chemical reaction can be predicted as a function of excess
chemical potential mN jmw e (m0 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 ux. The zero n
is relevant to the difussive chemical energy ux, and the nonzero n is
connected to the internal convective chemical energy ux.
In the presence of external chemical energy ge, Eq. (81) leads to
the differential equation in the four distinct regimes:
ge g kBT0 [(1/na)dgA/dm(1/nc)dgC/dm
 (1/nt)dgT/dm  (1/nf)dgF/dm].

(82)

(83)

In a process dominated by activation chemical energy, the differential equation for the chemical energy ux leads to
geA gA (kBT0/na) dgA/dm

(84)

where ge is the applied chemical energy ux to the solid wall.

Solving Eq. (84), we nd the chemical energy ux by convection
chemical energy, gA, given as a function of the excess chemical
potential mA:
gA g1A [1 e exp (namA/kBT0)]

mA jmw e (m0 maa)j,

mC jmw e (m0 mac)j,
mT jmw e (m0 mat)j,
mF jmw e (m0 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 reaction mechanism can be summarized as

m m0 maa  (kBT0/na) ln ZAge, m m0 mac  (kBT0/nc) ln ZCge,

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 ux which is proportional to
chemical potential difference. The total chemical energy ux is thus
expressed as the sum of the parallel chemical energy uxes:
g gA gC gT gF.

The rst term in the right hand side represents the Gibbs energy
ux due to activation chemical energy, the second the Gibbs energy
ux due to concentration, the third the Gibbs energy ux in transition chemical energy, and the fourth the Gibbs energy ux in lm
chemical energy. g1A, g1C, and g1F respectively indicate the limiting
Gibbs energy uxes in activation, concentration, and lm chemical
reactions.
We get the excess chemical potentials from the absolute activation chemical potentials in the four mechanisms:

(85)

where g1A geA. The limiting Gibbs energy ux at the activation

chemical potential of activation reaction maa is determined at the
end of the equilibrium process:
g1A g0 exp (namaa/kBT0).
We may apply the analogous schemes to the four control
mechanisms and establish the total Gibbs energy ux in an equation [30e36]. The total chemical energy ux can approximately be
given by the sum of chemical energy uxes in the four chemical
reaction regimes:

m m0 mat (kBT0/nt) ln ZTge, m m0 maf (kBT0/nf) ln ZFge,

(88)

where Zge 1  gm/g1m in the activation or cencentration chemical

reaction, Zge gm/g1m in the transition or lm chemical reaction, and
the limiting chemical energy ux g1m depends on chemical potential. Fig. 13 demonstrates schematic chemical energy uxes as a
function of excess chemical potential. The control mechanisms are
presented, and the maximum limiting state of concentration reaction 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
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 hydrogeneiodine reaction. During an activation reaction, a bimolecular
reaction takes place:
H2 I2 > 2HI.

(89)

During concentration and transition reaction, termolecular reaction

(or three body association reaction) proceeds:
I2 > 2I,
H2 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

1046

H.-S. Roh / Energy 89 (2015) 1029e1049

Fig. 13. Schematic chemical energy uxes 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 process is large. The process (90) is analogous to the transition in the
transition state theory [10e12], and the maximum limiting state of
concentration reaction corresponds to the transition state. Hydrogenebromine reaction, hydrogenechlorine reaction, hydrogeneoxygen reaction, and decomposition of nitrogen pentoxide
reaction are the analogous multi-step processes.
In the presence of the external chemical energy ux ge, the
temporal chemical energy transfer Eq. (25) yields
ge g (t/b) dg/dt

(91)

where t is the mean reaction time. From Eq. (91), the temporal
chemical energy ux has the integrated solution
g (tB) g1t [1 e exp (btB /t)].

(92)

We combine (86) and (92) and then nd the chemical energy ux in

activation chemical energy and concentration chemical energy
transfer:
g(m,t) g1A [1 e exp (namA/kBT0)] [1 e exp (ba tA/t)]
g1C [1 e exp (ncmC/kBT0)] [1 e exp (bc tC/t)]

(93)

where the temporal particle number constant ba in activation reactions is less than the temporal particle number constant bc in
concentration reactions, and the diffusion process in activation
reactions is slower than that in concentration reactions.
The excess times in the four chemical reaction mechanisms
indicate

tA t e (t0 taa),
tC t e (t0 tac),
tT t e (t0 tat),
tF t e (t0 taf),

(94)

where t0 is the global equilibrium time. taa, tac, tat, and taf are the
activation times for the four chemical reaction mechanisms. The
time in each chemical reaction mechanism is expressed as
t
t
t
t

t0
t0
t0
t0

taa  (t/ba) ln MA
e,
tac  (t/bc) ln MCe ,
tat (t/bt) ln MTe,
taf (t/bf) ln MFe,

(95)

where Me 1  gt/g1t in the activation or cencentration temporal

chemical reaction, Me gt/g1t in the transition or lm temporal
chemical reaction, and the limiting chemical energy ux g1t depends on time. Since the temporal particle number constant bc in
activation reactions is less than bn in concentration reactions, the
chemical process in activation reactions is slower than that in
concentration reactions.
Spatial behavior for the chemical energy ux is understood by
changing Eq. (26). In the presence of an external source we, it is
modied as
ge V$g (k/l) g (r).

(96)

Eq. (96) has the integrated solution

g (rB) g1r [1 e exp ((k/l) n$rB)]
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 k zB cosq/l and tan q kr/kz.
We nd the excess distances along the z axis in the four
chemical reaction mechanisms:
zA jz e (z0 zaa)j,
zC jz e (z0 zac)j,
zT jz e (z0 zat)j,
zF jz e (z0 zaf)j,

Fig. 14. Chemical energy transfer mechanisms. (a) As a function of chemical potential.
(b) As a function of distance.

(98)

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

and zaf are the activation distances for the four chemical reaction
mechanisms. The distance in each phase transition mechanism is
indicated as

H.-S. Roh / Energy 89 (2015) 1029e1049

z
z
z
z

z0
z0
z0
z0

zaa,
zac (l/kc) ln LCe ,
zat  (l/kt) ln LTe,
zaf  (l/kf) ln LFe,

(99)

where Le 1  gz/g1z in the cencentration spatial chemical reaction, Le gz/g1z in the transition or lm spatial chemical reaction,
and the limiting chemical energy ux 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
uxes 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 advantages of using chemical energy in multi-disciplinary elds.
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 efciency
is relatively high. In the following, a few broad scopes of the proposed 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,

1047

work transfer, and chemical energy transfer. In thermodynamic

energy transfer, the intensive variable changes such as temperature, 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 ux 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 justication of the postulate for the internal energy ux is
briey 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 independent parameters respectively. When we combine the knowledge from thermodynamics with fundamental quantities, we can
conrm that the entropy is an independent parameter as the corresponding extensive parameter of the temperature, the chemical
potential is an independent parameter as the corresponding
intensive parameter of the particle number, and the electric potential 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 ux u 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 claried. The two distinct mechanisms are separable in
generalized internal and external coordinates. The internal convective mechanisms of heat transfer, chemical energy transfer, and work
transfer are formulated based on empirical data in which each energy transfer is a function of its corresponding intensive variable.
Each energy ux 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 uxes are independent of the external space and
time coordinates in these internal convective mechanisms. The
internal degrees of freedom for temperature, pressure, and chemical 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 ux 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).

Fig. 15. Schematic diagrams of the chemical energy ux 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.

These energy uxes in conduction or diffusion mechanisms

explicitly depend on the external space and time coordinates.
As the explicit illustration of the chemical energy transfer theory proposed, the theory can be applied to several chemical reactions. It predicts multiple step reaction processes and their

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H.-S. Roh / Energy 89 (2015) 1029e1049

Table 6
Comparison among energy transfer processes.
Energy transfer

Heat transfer (solidication)

Heat transfer (boiling)

Work transfer

Electrochemical reaction

Chemical reaction

Conduction

Isothermal
Isentropic
Convection
Nucleation
Transient
Film

Isothermal
Isentropic
Convection
Nucleate
Transition
Film

Isobaric
Isochoric
Convection
Turbulence
Transition
Film

Diffusion
Migration
Activation
Concentration
Resistance
Film

Diffusion
Migration
Activation
Concentration
Transition
Film

Internal convection

corresponding process times. For example, we can consider the

hydrogeneiodine reaction. During an activation reaction, a bimolecular reaction takes place, and the reaction consists of the multiple processes. The reaction speed of the rst 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 theoretical 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 dened equations and are classied as quasiequilibrium 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, solidication, boiling, and liquidevapor phase transition [30e36]. In the kinetics of chemical
reactions, the four control mechanisms of activation, concentration,
transition, and lm 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 lm polarization. Likewise, solidication, 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 ux h:

l V$h  [T0 vh/v kBT0 vh/vm] t vh/vt 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 ux (enthalpy per unit
area and unit time):
h (, m, t, r) q()g(m)B(t)A(r) h0 exp (DH/kBT0) exp (bt/t) exp
(k$r/l)
where the temperature dependence reects an Arrhenius type
equation.

The Higgs mechanism [40] in quantum eld theory of physics is

the relativistic extension of the Ginzburg-Landau theory in nonrelativistic thermodynamics. This implies spontaneous symmetry
breaking mechanisms can be described by the Ginzburg-Landau
theory in thermodynamics. In the Ginzburg-Landau theory, the
scalar elds are recognized as the order parameters during phase
transitions. The scalar elds 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 multidisciplinary areas: For instance, endothermic or exothermic chemical reactions, biochemical reactions, polarization and electrodeposition, 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 nonequilibrium, quasi-equilibrium, and equilibrium at nite temperature. 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 unied 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 reactions regardless of their molecularity and order of reaction.
We apply the chemical energy transfer theory to nonequilibrium chemical reactions and discuss its logical predictions.
The four control mechanisms, three limiting uxes, and four activation parameters are adopted as input parameters. The four regimes formed as a function of chemical potential, time, and
distance are suggested analogously to electrochemical reactions:
activation, concentration, transition, and lm chemical reaction
regimes. The Gibbs energy uxes are predicted as a function of
chemical potential, time, and displacement.
The thermodynamic chemical energy transfer theory is indispensable 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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