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Kirchhoff's Law Can Be Exact

Preprint · May 2019

DOI: 10.48550/arXiv.1905.13574

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 Kirchhoff’s Current Law Can Be Exact
available at https://arxiv.org/abs/1905.13574

Robert S. Eisenberg
Department of Applied Mathematics
Illinois Institute of Technology;
arXiv: 1905.13574 July 17, 2019

Department of Physiology and Biophysics

Rush University Medical Center
Chicago IL
USA

Bob.Eisenberg@gmail.com

July 18, 2019

File name: Kirchhoff’s Current Law Can Be Exact July 16-4.docx

 Abstract

Kirchhoff’s current law is thought to describe the translational movement of

charged particles through resistors. But Kirchhoff’s law is widely used to
describe movements of current through resistors in high speed devices. Current
at high frequencies/short times involves much more than the translation of
particles. Transients abound. Augmentation of the resistors with ad hoc ‘stray’
capacitances is often used to introduce transients into models like those in real
resistors. But augmentation hides the underlying problem, rather than solves it:
the location, value and dielectric properties of the stray capacitances are not well
determined. Here, we suggest a more general approach, that is well determined.
If current is redefined as in Maxwell’s equations, independent of the properties
of dielectrics, Kirchhoff’s law is exact and transients arise automatically without
ambiguity. The transients in a particular real circuit—a high density integrated
circuit for example—can then be described by measured constitutive equations
together with Maxwell’s equations without the introduction of arbitrary circuit
elements.
 Kirchhoff’s current law says, in a crude representation, that the current that
flows into a node, must flow out. In textbooks, Kirchhoff’s current law describes
the translational movement of charges through resistors that might be called the flux
of electrons. The resistors are ideal, described by single real numbers. The current
is carried by charges that have mass, e.g., electrons, and the movements are slow,
without transients, nearly at DC [1-13].1
Kirchhoff’s law is used today to describe currents through resistors on the
nanosecond time scale. Indeed, it is the main design tool for the circuits of our high-
speed technology. The currents in high speed circuits have transients not seen when
movements are slow near DC. Current through resistors on the nanosecond time scale
involves delays and overshoots: it is a complex phenomena [14-22], not just the
movement of electrons in wires, in resistors or into capacitors. Kirchhoff’s current
law is viewed as approximate for these reasons, as is clear from its derivations [13,
14, 23, 24].
Engineers have dealt with these difficulties by ad hoc augmentation of DC
circuits [25]. They construct wideband circuit models made of
(1) idealized resistors with current strictly equal 𝑉𝑅 ⁄𝑅 , where 𝑅 is the
resistance and 𝑉𝑅 is the voltage across the resistor
in parallel with
(2) ideal capacitors, often characterized as stray [14, 26], sometimes as
‘parasitic’ [27].
These ideal capacitors carry currents strictly equal to 𝐶 𝜕𝑉 ⁄𝜕𝑡 , where
𝐶 is the capacitance, 𝑉 is the voltage across the capacitor and 𝑡 is time.
The size and location of the stray capacitances are chosen empirically
so the augmented circuits more or less fit measurements of high-speed
transients.
The values and locations of the stray capacitances are neither exact
nor unique. They are often crude approximations, because actual currents
deviate significantly from 𝐶 𝜕𝑉 ⁄𝜕𝑡 or 𝑉𝑅 ⁄𝑅 on the time scales of our
digital technology, in ways important in practice [18, 19, 21, 22, 28-34].

1
Sommerfeld [14], p. 101 describes the origin of Kirchhoff’s laws, as Kirchhoff’s solution to a problem posed in
a seminar led by Neumann.

3
Exact treatments have advantages. Empirical and imprecise modifications of a
circuit seem a poor substitute for an exact treatment, derivable from
electrodynamics, if that is possible.
An exact treatment is possible using a rederivation of the law of conservation
of current (eq. 3 below and ref. [25, 35-39]). We show (eq. 4, below) that Kirchhoff’s
law can be as exact as the Maxwell equations themselves2, once current is defined
as in the Maxwell equations, independent of the dielectric properties of matter [35-
37, 40].
The role of ‘current’ was evidently a key issue in Maxwell’s development of
electrodynamics, according to the historical literature [41-44]. Maxwell defined
current as we have, according to his successors at Trinity College Cambridge UK,
Jeans and Whittaker, [45], p.511; [46], p. 280, respectively. Lorrain and Corson [1],
p. 276 eq. 6-148, use that definition as well.

Current is usually defined as the flux of charge, although that is not the
definition used here, see eq. (3)-(4) below. The flux of charge is not conserved. It
accumulates in what are loosely called capacitors or stray capacitance. More
precisely, the flux of charge accumulates according to the ‘continuity equation’
described in textbooks of electrodynamics for the oversimplified case in which
single dielectric constant describes polarization [1, 2, 4, 5, 47].

Eq. 21-23 of ref [35] describes the effects of polarization on the accumulation
of charge in general materials. Ref [35] derives the continuity equation for materials
with complex polarization that cannot be described by a single dielectric constant.

Current in the Maxwell equations. Current appears in the equations of Maxwell

in his generalization of Ampere’s law.

Maxwell’s Version of Ampere’s Law

1 𝜕𝐄
𝐜𝐮𝐫𝐥 𝐁 = 𝐉 + 𝜀0 (1)
𝜇𝑜 𝜕𝑡
𝜕𝐄
𝐉 = (𝜀𝑟 − 1)𝜀0 + 𝐉𝒆𝒗𝒆𝒓𝒚𝒕𝒉𝒊𝒏𝒈 𝒆𝒍𝒔𝒆 (2)
𝜕𝑡

2
Ref [19-23, 37, 41-43] apply the Maxwell equations within atoms using Bohm’s version of quantum
mechanics.

4
 See texts [1, 2, 4, 5, 47] for the standard formulation of Maxwell’s equations.
See ref. [35] for an update to Maxwell’s equation that includes a more realistic (and
general) description of polarization and permanent charge (not present in Maxwell’s
original formulation). 𝜀0 𝜕𝐄⁄𝜕𝑡 is written separately in eq. (1) because it is a
property of space, not matter, as discussed below. The variable 𝜀𝑟 − 1 and
𝐉𝒆𝒗𝒆𝒓𝒚𝒕𝒉𝒊𝒏𝒈 𝒆𝒍𝒔𝒆 are properties of matter, not space, see below on p. 6.
𝐁 describes the magnetic field with magnetic constant (permeability of
vacuum) 𝜇𝑜 . 𝐄 describes the electric field, with electric constant 𝜀0 (permittivity of
vacuum). 𝜀𝑟 is the relative dielectric coefficient of perfect dielectrics, a single real
positive constant ≥ 1. 𝐉 is the current produced by all translation of mass—
including all movements of mass with charge, however small or transient the
movement. 𝐉 includes the polarization currents of dielectrics, ideal and real. The
polarization of idealized dielectrics (𝜀𝑟 − 1)𝜀0 𝜕𝐄⁄𝜕𝑡 is isolated from other
currents in eq. (2) only for convenience in relating our results to the literature [2, 5,
47-55]. Most of the literature of electrodynamics is written as if all dielectrics are
ideal; Robinson [56] is a welcome exception that most resembles the treatment here.
Eq. (1)-(2) require a complete description of 𝐉. A set of experimental results can
serve this purpose. Theories or simulations of 𝐉 can also serve this purpose if they
fit the experimental data.3
𝐉 includes charge carried by the flux of particles, as in most textbooks.
𝐉𝒆𝒗𝒆𝒓𝒚𝒕𝒉𝒊𝒏𝒈 𝒆𝒍𝒔𝒆 includes the flux of particles and the nonideal polarization of real
materials. It also includes other movements of charge, described below, and
quantum effects [18-22, 36, 57-59] although those are not our focus.

Current. The current described as ‘Everything else’ in eq. (2) includes current
produced by
(1) transport (flux) of electrons or charged particles, as in classical Kirchhoff’s
law of DC (or low frequency) circuit analysis.
‘Everything else’ also includes
(2) the nonideal properties of dielectrics;

3
Those theories and simulations are most useful if they are transferable from one set of experimental conditions
to another, using just one set of parameters. Not all theories and simulations have that property (see the note [61]
and its documentation in [62]). In chemical kinetics, parameters are customarily adjusted as conditions change so
a favored equation —the law of mass action—always fits data.

5
 (3) polarization of matter in general, time dependent, nonlinear or whatever;
(4) currents driven by other fields, like diffusion, heat, and convection;
(5) any other movement (of any type) of charge with mass, including quantum
effects [18-22, 36, 57-59].
‘Everything else’ does not include
(6) the properties of dielectrics idealized by (𝜀𝑟 − 1) 𝜀0 𝜕𝐄⁄𝜕𝑡. That is treated
separately as is the custom in the classical literature and textbooks.
(7) the polarization of the vacuum 𝜀0 𝜕𝐄⁄𝜕𝑡. That ethereal current is written
separately from 𝐉 and 𝐉𝒆𝒗𝒆𝒓𝒚𝒕𝒉𝒊𝒏𝒈 𝒆𝒍𝒔𝒆 in eq. (2).

Polarization of the vacuum. The term 𝜀0 𝜕𝐄⁄𝜕𝑡 is treated separately because it has
such a different origin. 𝜀0 𝜕𝐄⁄𝜕𝑡 describes the ‘polarization of the vacuum’ [35]
that allows—or should one say ‘supports’ ? —the ethereal propagation of
electromagnetic waves through a vacuum devoid of mass. The polarization of the
vacuum is a consequence of general physical laws [2, 47, 49, 50, 60-62], not a
property of matter, and should really be called ‘the polarization of space’. The
polarization 𝜀0 𝜕𝐄⁄𝜕𝑡 makes charge relativistically invariant, independent of
velocity, even at velocities approaching the speed of light. References include p. 553
of [2] ; p. 228, eq. 5-110, of [1] and [47, 50, 60, 63, 64].
Charge is different from mass, length, and time, and most fundamental
quantities. They vary with velocity according to the Lorentz transformation. Charge
does not [2, 47, 49, 50, 60-62].
Polarization of real materials. Polarization of real materials is too complex to
approximate usefully with a constant 𝜀𝑟 [40]. Polarization is nonlinear in significant
applications, particularly optical [56, 65-70]. Even when the polarization is linear,
it involves complicated delays and varies too much with conditions and
frequency/time to allow description with a constant 𝜀𝑟 .
An abundant and classical literature—prominent since at least 1928 [71, 72]—
reports the actual properties of polarization of real dielectrics. Most of the classical
literature concerns polarization that is proportional to the local electric field, i.e. that
is linear [36, 71-100]. Polarization has been studied in great detail because it is a
major determinant of the forces between molecules [101, 102].
Parsegian [101] discusses at length (and with admirable clarity) the connection
between polarization and the spectra observed when light interacts with molecules.
Spectra are used to identify molecules—more or less as successfully as fingerprints
identify people—because spectra (and polarization) are sensitive to details of
chemical structure and thus are remarkably diverse, almost as diverse as the

6
molecules themselves [101, 103-107]. The diverse polarization and spectra of real
materials obviously cannot be described by a single number or dielectric constant.
Despite this literature, 𝜀𝑟 has been treated as a single real positive constant ≥ 1
in textbooks of electrodynamics [1-5, 47, 49, 50, 61, 62] for many years apparently
following [108, 109]. Robinson [56] is a welcome exception.
The properties of charge movement in matter are so complex that Feynman
concluded that nothing much could be said in general (on p. 10-7 of [5]). It is
necessary “… to exhibit in every case all the charges, whatever their origin, [so] the
equations [of electrodynamics] are always correct.” In fact, something important
can be said about electrodynamics in general, independent of the properties of
matter. Current, as defined by Maxwell, is universally conserved [35-39].
Conservation of current can be derived without reference to matter:
Conservation of current 𝐉𝒕𝒐𝒕𝒂𝒍 is in fact a general and exact property of the Maxwell
equations, as general as the Maxwell equations themselves, independent of any
properties of matter [35-39]. The dielectric constant 𝜀𝑟 is not involved in the
derivation of conservation of current at all. The derivation involves no statement or
approximation to dielectric properties or polarization, nonlinear or linear, or any
other properties of matter whatsoever.
Conservation of current. A general statement of conservation of current—eq. (3)
below—can be derived [35-39] because the divergence of the curl in eq. (1) is
identically zero, independent of any properties of matter, whenever Maxwell’s
equations can be used. The crucial term that produces universal conservation of
current is the polarization of space 𝜀0 𝜕𝐄⁄𝜕𝑡. The polarization of space has nothing
to do with matter because 𝜀0 has nothing to do with matter. 𝜀0 is a property of space,
not matter.
Physically, the polarization of the vacuum creates the ethereal current 𝜀0 𝜕𝐄⁄𝜕𝑡.
The ethereal current is an output of the Maxwell equations that varies so the total
current 𝐉𝒕𝒐𝒕𝒂𝒍 = 𝐉 + 𝜀0 𝜕𝐄⁄𝜕𝑡 is conserved [35]. The ethereal current allows
current to be conserved no matter what physics is involved in the translation
of matter and charge—see eq. 4 of [39] and Fig. 2 of [37]—even quantum physics
(see eq. 45 of [36]).

𝐉𝒕𝒐𝒕𝒂𝒍 = 𝑪𝒖𝒓𝒓𝒆𝒏𝒕
⏞ 𝜕𝐄
Conservation of Current 𝐝𝐢𝐯 𝐉 + 𝜀0 =0 (3)
𝜕𝑡
( )

7
Novel derivation, apparently. This general statement of conservation of current is
not easily found in textbooks or the literature of electrodynamics.
The usual derivations of conservation of current (and the continuity equation
derived in [35]) involve the dielectric constant 𝜀𝑟 and treat it as a single real constant
number in contradiction to experimental measurements of dielectric properties [36,
71-100], spectra [103-107, 110], and nonlinear polarization [56, 65-70], as
mentioned before.
Derivations of conservation of current do not usually deal with the sum labelled
‘Current’ in eq. (3). They do not usually deal with 𝐉𝒕𝒐𝒕𝒂𝒍 = 𝐉 + 𝜀0 𝜕𝐄⁄𝜕𝑡. The usual
derivations deal with 𝐉. Examination of eq. (3) shows that 𝐉 is not universally
conserved (because it neglects the ethereal current 𝜀0 𝜕𝐄⁄𝜕𝑡 ). 𝐉 accumulates in
systems, capacitors and stray capacitances as specified precisely by the continuity
equation. 𝐉𝒕𝒐𝒕𝒂𝒍 does not accumulate.
It is no wonder then that readers of the usual derivations, and most scientists,
conclude (incorrectly) that conservation of current is a poor approximation that does
not fit experimental data.
Conservation of total current is not an approximation when total current is
defined as 𝐉𝒕𝒐𝒕𝒂𝒍 because 𝐉𝒕𝒐𝒕𝒂𝒍 includes the ethereal current 𝜀0 , as shown in [35-
39]. 𝐉𝒕𝒐𝒕𝒂𝒍 is conserved. 𝐉 is not.
Kirchhoff’s current law is the general conservation law eq. (3) rewritten for
branched one dimensional networks.4 One dimensional networks have the special
property that 𝐜𝐮𝐫𝐥 𝐁 = 0, as is apparent if one writes out the curl operator explicitly
in one dimension [111, 112]. Kirchoff’s law then does not involve current flows or
coupling induced by the magnetic field. Those phenomena occur in three
dimensional problems and could be quite significant in rapidly changing signals,
like those of modern integrated circuits if the circuits involved three dimensional
flows of current. If the flows of current are one dimensional, phenomena mediated
only by the magnetic field are not significant because 𝐜𝐮𝐫𝐥 𝐁 = 0 in one
dimensional circuits.
Kirchoff’s law is widely viewed as an approximation, needing derivation; see
p. 8-10 of [14] and [13, 23, 24] for some derivations, along with less precise

4
The precise definition of a network involves many issues beyond the scope of this paper [(6-12, 15-
18, 114, 115].

8
discussions in most textbooks describing circuits. But Kirchhoff’s law need not be
approximate if current is defined5 to include the ethereal term 𝜀0 𝜕𝐄⁄𝜕𝑡 [35-39].

𝜕𝐄
Proposed Definition: 𝐂𝐮𝐫𝐫𝐞𝐧𝐭 ≜ 𝐉𝒕𝒐𝒕𝒂𝒍 = 𝐉 + 𝜀0 (4)
𝜕𝑡

With this definition of 𝐉𝒕𝒐𝒕𝒂𝒍 , all the current that flows into a node, flows out,
exactly, at any time, no matter how brief, under all conditions in which the Maxwell
equations apply. It is exactly conserved. It cannot accumulate at all. It cannot be
stored. In the language of fluid dynamics, the electric current 𝐉𝒕𝒐𝒕𝒂𝒍 is the flow of
an (exactly and perfectly) incompressible fluid.
The incompressible fluids of hydrodynamics are, on the other hand, an
approximation, and not a very precise one if one thinks of the dynamic range of
electrical approximations (which are at least 107 : 1 in real circuits and
immeasurably large in systems with little matter, as in the space between stars). The
incompressible flow 𝐉𝒕𝒐𝒕𝒂𝒍 is not approximate.
𝐉𝒕𝒐𝒕𝒂𝒍 is as incompressible as Maxwell’s equations are exact. It is perfectly
incompressible under all conditions in which the ethereal current 𝜀0 𝜕𝐄⁄𝜕𝑡 is a
perfect description of the physics of space, i.e. whenever Maxwell’s equations are
exact.
The question of what flow is described by 𝐉𝒕𝒐𝒕𝒂𝒍 has received a great deal of
attention from Maxwell and other workers, particularly in the special case of flow
in a vacuum 𝐉𝒕𝒐𝒕𝒂𝒍 (𝐯𝐚𝐜𝐮𝐮𝐦) = 𝜀0 𝜕𝐄⁄𝜕𝑡 as described in Whittaker’s “A History of
the Theories of Aether & Electricity” [46]. The properties of the “luminiferous
(a)ether” need not concern us as long as the equations describing the flow
𝐉𝒕𝒐𝒕𝒂𝒍 (𝐯𝐚𝐜𝐮𝐮𝐦) are correct, in the sense that they describe the properties of
electromagnetic radiation in empty space, and mathematically consistent.
The question of what flows in the vacuum is too vacuous and too ethereal to
grasp, in my opinion, because the crucial 𝜀0 𝜕𝐄⁄𝜕𝑡 term is a property of space, not
matter. No one knows (as far as I can tell) how space can flow. From the point of
view of mathematics, the meaning of the flow 𝐉𝒕𝒐𝒕𝒂𝒍 (vacuum) is determined by the
properties of space and time, described by special and general relativity, as charge

5
Lorrain and Corson [1], p. 276 eq. 6-148, use this definition of current. As far as I can tell, they do not
discuss the approximate nature of 𝜀𝑟 . If the approximate nature of 𝜀𝑟 is not discussed, the reader will
then naturally think (incorrectly) that conservation of current is as unrealistic as the idealization of a
single dielectric constant. The development of Robinson [57] does not depend on the approximate nature
of 𝜀𝑟 , but as far as I can tell, it does not use the definition of current of eq. (4).

9
moves and the electric field evolves according to the Lorentz transformation [2, 47,
49, 50, 60-62].
Ordinary Definition of Current. Current is defined in many textbooks as the
charge carried by the translation of charged particles [2, 5-8, 11, 12, 14, 15, 17, 47-
55, 113, 114]. This ordinary translational current is just part of the current 𝐉𝒕𝒐𝒕𝒂𝒍
defined here in eq. (4). Another part of the current is classical, namely the current
through an ideal dielectric (𝜀𝑟 − 1) 𝜀0 𝜕𝐄⁄𝜕𝑡 found in eq. (2).
The current ordinarily defined in textbooks is not conserved. The continuity
equation found in most textbooks of electrodynamics shows explicitly how charge
accumulates so current (as ordinarily defined) is not conserved. In crude language,
current can accumulate in capacitors and so is not conserved. Those capacitors
include the ‘capacitance of empty space’ arising from 𝜀0 . In more precise language,
current accumulates in polarization according to the continuity equation written in
various forms in eq. 21-23 of ref [35], appropriate for the complicated properties of
polarization in real materials. The continuity equation for the flow of mass is of
course also involved and must be included in a description of a coupled system.
We use Maxwell’s definition of current 𝐉𝒕𝒐𝒕𝒂𝒍 of eq. (4) precisely to avoid these
difficulties. 𝐉𝒕𝒐𝒕𝒂𝒍 does not accumulate, ever, anywhere. It is perfectly conserved.
All the 𝐉𝒕𝒐𝒕𝒂𝒍 that flows into a node flows out, always, everywhere.
The ordinary definition of current as only the flux of charged particles causes
practical difficulty in Kirchhoff’s law when applied to high speed circuits made only
of idealized resistors (described by constant real numbers) [13, 14, 23-25]. Such
idealized circuits do not have the transients, delays, or overshoots found in real
circuits made of resistors [18, 23, 24, 28-34]. Idealized circuits cannot deal with the
actual behavior of circuits observed on the nanosecond time scale if they use the
ordinary statement of Kirchhoff’s law and the ordinary definition of current as 𝐉. Of
course, the idealized circuits can be made more realistic by adding fictitious circuit
elements.
Stray Capacitances. Engineers routinely add such fictitious capacitances to circuit
models that include idealized resistors [25], so the transients of the idealized,
augmented circuit approximate those observed in real circuits [26, 27]. The fictitious
capacitances are not actual distinct circuit components. The location and values of
the fictitious stray capacitances are chosen by the engineer to fit data and are rarely
derived from electrodynamics.
The redefinition of current by equation (4) produces transients that are
determined precisely without fictitious capacitances. Reference [25], eq. 14, shows
how to choose capacitances arising from 𝜀0 𝜕𝐄⁄𝜕𝑡 , once current is defined by eq. 4.

10
 Transients in real circuits are more complicated than those predicted in
reference [25]. Reference [41] shows how to include any types of current flow—
polarization, inductive, or anything else—in the analysis, so the theory can cope
with the properties of real circuit boards.
Polarization of real circuit boards involves more than 𝜀𝑟 𝜀0 𝜕𝐄⁄𝜕𝑡 on the time
scales of practical importance in our digital technology. Inductive effects of wires
[20-24]; capacitances arising from materials like circuit boards [28-33]; and the
complex geometry of the real circuit contribute additional terms beyond those
arising from 𝜀0 𝜕𝐄⁄𝜕𝑡 or (𝜀𝑟 − 1)𝜀0 𝜕𝐄⁄𝜕𝑡 . The polarization in models of real
circuits needs to be determined from measurements of real circuit boards because
polarization is likely to depend on details of composition and construction of the
real circuits, and perhaps on the signals themselves. Reference [41] shows how to
include any polarization in the analysis, so it can describe real circuit boards.
Role of the B field. The lack of magnetic field B in branched one dimensional
circuits is discussed at length in [35] where the speculation is made that the absence
of B fields makes circuit design (at high speeds) much easier. B fields produce ‘leaks
of current’ and cross talk that are difficult to deal with in circuit design, particularly
because they are so variable and dependent on properties of the signals themselves,
as well as details of layout, etc.
It seems to me that ground planes in high speed circuits might function better—
i.e., more ideally, obeying the DC version of Kirchoff’s law more accurately—if they
too were built as branched one dimensional circuits, with minimal B fields, cross
talk, and current leakage in the grounds.
Conclusion. Stray capacitances, of unknown value, location, and unrealistic
properties seem a poor substitute for currents defined exactly by the Maxwell
equations. Transients arise naturally if current in Kirchhoff’s law is defined as in
Maxwell’s equation, see eq. (1)-(4). Realistic transients, arising from nonideal
properties of circuits, can be easily incorporated into our treatment [35].

11
 Appendix
Networks of Chemical Reactions
Our discussion has focused on Kirchhoff’s law in electrical networks. Networks
and analogs of Kirchhoff’s law are also used widely to describe interacting chemical
reactions in chemistry, biochemistry and biology [115-122]. The hundreds of
enzyme reactions in the intermediary metabolism that form ‘the chemical factory of
life’ are a notable example. These networks of chemical reactions are used by
thousands of scientists every day to explain medical and biological phenomena and
appear in every textbook of physiology, biochemistry, molecular and cell biology,
and medicine.
Chemical networks. Equations of chemical [115-120] and enzyme kinetics [121,
122] use analogs of Kirchhoff’s law to connect chemical reactions. The analogs
describe the flux of particles, not the flow of electric current. The analog equations
use conservation of mass but rarely mention or use conservation of current. They do
not include an 𝜀r 𝜀0 𝜕𝐄⁄𝜕𝑡 term and so cannot conserve 𝐉𝒕𝒐𝒕𝒂𝒍 . They also do not
conserve 𝐉𝒕𝒐𝒕𝒂𝒍 in the steady-state, as is clear by using the law of mass action of
chemical reactions to compute and compare steady state currents for reactions in
series [35, 37, 123, 124].
Auxiliary conditions may be possible that make equal the current 𝐉𝒕𝒐𝒕𝒂𝒍 in a series
of chemical reactions but auxiliary conditions are not found in the standard
references [115-122] or textbooks, simple or advanced, as far as I know. The
implication is that the treatment of chemical reactions in a wide range of the
chemical and biological literature is incompatible with the Maxwell equations. One
consequence may be the well known need to adjust parameters of chemical reactions
as reactions are transferred from one set of conditions to another. Descriptions of
chemical reactions are expected to be transferable only if they describe the real
world properties of the reactants [35, 37, 123, 124], including its electrodynamics.
The real world is different from the world of textbooks, or chemical reaction
theory because the real world follows Maxwell’s equations universally, at all
locations and times, and under all conditions in which chemical reactions are
studied. In the real world, the atomic scale electric field in one reaction is influenced
by distant reactions—and by even more distant macroscopic boundary conditions—
to create ‘flux coupling’ that would not be present without this long range influence
of the electric field. Rate ‘constants’ of a series of reactions are coupled even for
chemical reactions that are distinct and disjoint in space, far apart on an atomic
length scale, occurring in different structures.
The auxiliary equations needed to conserve current 𝐉𝒕𝒐𝒕𝒂𝒍 interact with the
equations of chemical kinetics that conserve mass. One set of conservation laws is

12
not enough. Both must be solved together. One way to do this is to write separate
networks for electric current and for mass flow.
The networks for conservation of mass and conservation of current 𝐉𝒕𝒐𝒕𝒂𝒍
together can be solved with the methods of the theory of complex fluids which are
designed to deal with multiple simultaneous force and flow fields. In particular, the
variational method of complex fluids [125-136] may allow one to create a new
synthetic composite functional with units of energy. In this way, flux coupling can
be dealt with consistently on all scales, i.e., with all variables satisfying all boundary
conditions with one set of unchanging parameters.
Flux coupling plays a central role in many transport systems and chemical reactions
in biology. Flux coupling allows the ‘unnatural’ uphill transport of ions (and solutes)
to be driven by the natural downhill movement of other ions (and solutes). Active
transport of this sort occurs throughout biological cells and organelles and is one of
the fundamental mechanisms of life.
Flux coupling is a central mechanism in oxidative phosphorylation and
photosynthesis, which are the ultimate source of the energy for life, whether the
energy is used in chemical, electrical, or diffusional processes. In oxidative
phosphorylation and photosynthesis, electron flow is coupled to the movement of
ions and ‘protons’ across membranes of mitochondria.6 Flux coupling in oxidative
phosphorylation, and in photosynthesis, are particular examples of a general
phenomenon. Flux coupling comes from a combination of macroscopic and atomic
scale phenomena involving their mutually generated electric field, as well as
(perhaps) chemical interactions.
Flux coupling depends on the experimental conditions. Flux coupling depends
on anything that can change the macroscopic electric field. In particular, flux
coupling depends on the boundary conditions.
Boundary conditions are different in different setups used to measure flux and
flux coupling. Some setups leave the system in its natural state, with
transporters/channels in native structures, like mitochondria. Other setups insert the
transporter/channel into a lipid bilayer.
Flux coupling will be different in the two setups because they impose different
boundary conditions. In mitochondria, the sum of currents across a membrane is
zero (as it is in cells or organelles shorter than a length constant or so [137]). The
biological situation imposes the condition that the sum of all currents across the
membrane is zero, because structures, like mitochondria, are so small.

6
‘Proton’ is a nickname for the positively charged form of water, sometimes written as H3 O+.

13
 Transporters are often studied, however, in non-native bilayer setups where
currents are only constrained by the applied electrical and chemical potential
(i.e., concentrations). Quite different results for flux coupling can occur in that case,
quite different from the flux coupling that is found in the mitochondria, because the
constraints on the fluxes (the boundary conditions produced by conservation of
current) are so different.
Flux Coupling and Channel Opening. Manuel Landstorfer and I recently realized
[36] that a different kind of coupling can occur between the voltage sensor of a
voltage sensitive channel [138-143] and its conduction pore. Part of the current
injected by the voltage sensor might flow through the conduction pore and trigger
its opening.
Similarly, flux coupling can occur when a transmitter binds to a receptor on a
channel protein, like acetylcholine binding to the acetylcholine channel. Binding of
a charged agonist to a charged receptor produces current and some of that current
can be injected into the conduction pore, triggering its opening, even though the
pore is far away from the receptor.
Historical Note. The reason 𝐉𝒕𝒐𝒕𝒂𝒍 is not conserved in chemical kinetics [115-122]
is historical, I suspect. Chemists were understandably focused on mass and its
transformations not electric current and its flow. Conservation of mass is used in the
derivation of the equations of enzyme kinetics, but conservation of current is not
mentioned, to the best of my knowledge.
Mass can accumulate according to the continuity equation of fluid dynamics.
Chemical kinetics allows accumulation of mass this way but is silent about
conservation of charge or current, whether steady-state or transient. Charge can
accumulate according to the continuity equation for 𝐉 shown in various forms in
eq. 21-23 of [35]. In contrast, the Maxwell equations do not allow accumulation of
the current 𝐉𝒕𝒐𝒕𝒂𝒍 , whether steady-state or transient, not at all, not under any
conditions or at any time. All the 𝐉𝒕𝒐𝒕𝒂𝒍 that flows into a node flows out.
Conclusion. It seems wise to use network models in both chemistry and electronics
that conserve 𝐉𝒕𝒐𝒕𝒂𝒍 with as few ad hoc extensions to Maxwell’s equations as
possible: the artifacts in electrical potential and fluxes can be very large if current is
not conserved. The artifact in the electric potential is large, because of the strength
of the electric field (see the first page of Feynman [5] and Appendix of [37]). Fluxes
often flow over large barriers, where flux is an exponential function of potential.
Flux artifacts can then be exponentially large and are best avoided. Models with
large artifacts are unlikely to be transferrable from one of conditions to another.

14
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