HYLE International Journal for Philosophy of Chemistry, Vol. 18 (!1", #o. , 1$%&1'(.

Copyri)ht !1 *y HYLE an+ Hinne Hettema.

The Unity of Chemistry and Physics:
Absolute Reaction Rate Theory
Hinne Hettema
Abstract: Henry Eyrings absolute rate theory explains the size of chemical re-
action rate constants in terms of thermodynamics, statistical mechanics, and
quantum chemistry. In addition it uses a number of unique concepts such as
the transition state. !ey feature of the theory is that the explanation it pro-
"ides relies on the comparison of reaction rate constant expressions deri"ed
from these indi"idual theories. In this paper, the example is used to de"elop a
naturalized notion of reduction and the unity of science. #his characterization
pro"ides the necessary clues to the sort of inter-theoretic lin!ages that are pre-
sent in the theory of reaction rates. #he o"erall theory is then further charac-
terized as a theory net$or!, establishing connections bet$een non-reducti"e
notions of inter-theory connections. #his characterization also sheds ne$
light on the unity of science.
Keywords: re+u,tion of ,hemistry to physi,s, unity of s,ien,e, ,hemi,al -ineti,s,
a*solute theory of rea,tion rates, e.planation.
Introduction
#he unity of chemistry and physics should be paradigmatic for the unity of
science. %ith the ad"ent of atomic theory, quantum theory, and statistical
mechanics, the fields of chemistry and physics ha"e become increasingly in-
tert$ined, perhaps e"en up to the point $here, as &eedham '()*)+ argues, it
$ould be hard to imagine chemistry $ith the physics remo"ed. Hence it is a
"alid question to as! ho$ this unity of science is constituted in terms of the
inter-relationship bet$een theories. In the present paper, these inter-relations
$ill be considered for theories of chemistry and physics, specifically focusing
on Eyrings theory of absolute reaction rates.
#here seems to be a significant di"ergence of approaches bet$een general
philosophers of science and philosophers of chemistry in the consideration of
these issues.
*,- Hinne Hettema
In the *./)s and *.-)s, many philosophers of science argued that some
form of theory re+u,tion pro"ides the glue that holds the different sciences
together. Ho$e"er, the exact shape and form that this reduction might ta!e
has been left far from settled, and currently there exist multiple opinions and
confusions about $hat reduction exactly is. 0or instance, $hile the most
popular notion of reduction is that of &agel '*.-*+, the exact shape and form
of theory reduction that $as actually ad"ocated by &agel is commonly mis-
understood.
0or many philosophers, &agelian reduction has become identical $ith the
strict "ersion of it ad"ocated in 1ausey '*.22+, $hich turns the &agelian
theory into a form of reductionism based on both ontological reductionism
and strict deri"ation. 3ecently, the papers by 0aze!as '()).+, 4lein '()).+,
5izad6i-7ahmani, 0rigg 8 Hartmann '()*)+ and "an 3iel '()**+ ha"e argued
that this form of reduction $as actually not ad"ocated by &agel, but that
&agel instead argued for a more moderate form of reduction that is perhaps
best characterized as a formal paraphrase of the explanation of la$s and theo-
ries by other theories.
In addition to reduction, philosophers of s,ien,e ha"e de"eloped non-
reducti"e notions of the unity of science, often inspired by specific episodes
in the history of science. Examples of such non-reducti"e approaches are ad-
"ocated by 5arden 8 9aull '*.22+, 7o!ulich '()):+, and &eurath '*.:;a,b+.
#hese approaches to the inter-theory relationship ha"e not been $idely used
in the philosophy of chemistry, but ha"e the potential to pro"ide interesting
additional insights.
<hilosophers of ,hemistry, partly in response to the percei"ed problems
associated $ith the strict interpretation of the &agelian model of reduction
ha"e also de"eloped a number of alternati"e approaches to the problems
posed by the inter-relationship bet$een theories of chemistry and physics.
mong the proposals so far are a <opperian notion of reduction as explana-
tion ad"ocated by =cerri '*..:+, a notion of the relation as one of emergence,
e"en $ith a degree of bac!$ard causation 'see Hendry ()*)+, "arious pro-
posals for ontological reduction 'see >e<oide"in ())/, =cerri ())2, >ombar-
di 8 >abarca ())/, and >abarca and >ombardi ()*) for a discussion+, as $ell
as an argument for a 5uhemian account of the unity of science proposed by
&eedham '()*)+.
Hence it $ould seem that there is not a broad o"erlap in approaches be-
t$een the philosophy of science and the philosophy of chemistry. #he pro-
posals for the inter-theory relationship bet$een theories of chemistry and
physics $hich originated in the philosophy of chemistry seem to ha"e o"er-
loo!ed some of the semi- and non-reducti"e proposals $hich ha"e gained
significant traction in the general philosophy of science, and, /i,e /ersa, the
0he 1nity of Chemistry an+ Physi,s *,2
proposals of philosophers of chemistry ha"e largely been o"erloo!ed by the
general philosophy of science community.
1omplicating matters is that the $idespread re6ection of reduction by
philosophers of chemistry might ha"e been premature. #he reduction of
chemistry to physics is usually discussed from the "ie$point of fairly simple
chemical theories $ith a simplified notion of reduction, usually of the
&agel?1ausey type. It is no$ a fairly common contention in the philosophy
of chemistry that chemical theories pro"ide little or no support for a strict
notion of reduction of the &agel?1ausey type, and this has been one of the
main forces dri"ing philosophers of chemistry to find alternati"e conceptions
of the inter-relationship bet$een theories of chemistry and physics, ap-
proaches $hich in turn ha"e not been generalized to pro"ide a more compre-
hensi"e theory of the unity of science.
In this paper I argue that the theory of chemical reaction rates, and espe-
cially Eyrings theory of absolute reaction rates '$hich is often called abso-
lute reaction rate theory to contrast it $ith theories that do not pro"ide in-
terpretations for some of the terms in the rrhenius equation or transition
state theory because it introduces a ne$ term in chemical terminology+, pro-
"ides a number of ne$ insights into a realistic notion of the sort of unity of
the sciences that exists bet$een physics and chemistry. It can thereby help
o"ercome the barrier bet$een philosophy of science and philosophy of
chemistry on the one hand, and propose a number of interesting reconcilia-
tions bet$een reducti"e and non-reducti"e notions of the unity of science, on
the other hand.
0ocusing on reduction, I in"estigate $hat it ta!es to e.plain a particular
chemical theory 'rrhenius equation for reaction rate constants+ in terms of
'a number of+ physical theories, and ho$ a reduction bet$een these theories
might $or!. I then discuss the prospects of non-reducti"e theories of the
unity of science. #he conclusion is that Eyrings theory of absolute reaction
rates does not quite fit $ith either reducti"e or non-reducti"e approaches
for t$o reasons.
In the first place, the theory introduces a specific ne$ concept, the transi&
tion state, into the lexicon. #his ne$ concept is the result of the addition of
specific conditions to the reducing theory, as $ell as the detailed formulation
of local assumptions about the nature of chemical reactions at a micro le"el.
#he transition state is defined $ith a significant degree of conceptual clarity
and precision, gi"es the theory considerable explanatory po$er, and is to a
large extent responsible for the continued conceptual success of the theory.
#raditional theories of reduction do not usually foresee such introductions of
ne$ concepts, though, as I $ill argue, $ith some close reading of its original
intentions, &agels model for reduction can be made to fit the bill.
*,: Hinne Hettema
=econdly, the theory critically depends on multiple candidates for reduc-
ing theories $hich each add critical elements to create the final theory of
absolute reaction rates, and part of the process of the de"elopment of the
theory is that it allo$s for the interpretation of some of its terms in the ter-
minology of different reducing theories.
Hence the o"erall explanatory structure is explanation in terms of a net-
$or! of theories, in $hich &agelian lin!ages can be characterized as theoreti-
cal patches that pro"ide the net$or! connections. #his is a situation that I
belie"e is fairly common in chemistry, but currently not $idely in"estigated
in theories of reduction. Hence it is important that this structure is charac-
terized and discussed in order to ad"ance the debate on the unity of chemis-
try and physics.
#he fact that the theory of absolute reaction rates has sufficient complexi-
ty to represent a real-life scientific theory, rather than a toy theory, therefore
suggests that it is a good example of realistic inter-theory relations bet$een
chemistry and physics.
It is primarily the aim of this paper to e"aluate the absolute reaction rate
theory as an e.ample for the unity of s,ien,e so that some long held theories of
reduction, as $ell as non-reducti"e approaches, can be usefully compared
against a realistic record.
#his paper is structured as follo$s. In the next section, =ection (, I lay out
the mathematical and conceptual structure of reaction rate theory. =ection ;
outlines in some detail the rele"ant aspects of the theory of reduction, from
the "ie$point of &agel and his critics. #his section contains my reasons for
the proposed liberal reading of &agel, but other$ise contains little ne$ mate-
rial and may be s!ipped by readers that are familiar $ith the literature on re-
duction. In =ection ;.(, I pro"ide an introduction to some non-reducti"e ap-
proaches. I ma!e a proposal for naturalized reduction in section ;.;. #hen I
continue, in =ection ,, $ith a characterization of Eyrings theory of absolute
reaction rates as an example of naturalized reduction. =ection / contains a
conclusion that dra$s the main lines together.
#he treatment of the material in this paper is informal, focusing on the
o"erall structure of the theory of absolute reaction rates. formal rendering
of naturalized reduction relationships is presented in Hettema ()*(.
(. 3eaction 3ate #heory@ its history and structure
#he theory of absolute reaction rates $as de"eloped by Henry Eyring '*.;/+,
and $as discussed in detail in a boo! by Alasstone, >aidler 8 Eyring '*.,*+.
Eyring, %alter 8 4imball '*.,,+ discussed the theory in a single chapter,
0he 1nity of Chemistry an+ Physi,s *,.
adding a quantum mechanical formulation of the theory. #he historical de-
"elopment of the theory is presented in >aidler 8 4ing *.:; as $ell as in 9il-
ler *..:. I follo$ primarily Alasstone et al. *.,*, and note that >aidler 8
4ing *.:; contains a number of useful additions to my presentation. In this
section it is my aim to trace the de"elopment of the theory of absolute reac-
tion rates from the rrhenius equation to the formulation in Eyring *.;/ and
Alasstone et al. *.,* in a limited "ersion.
If $e consider a chemical reaction
B 7 B ... 1 B 5 B ...
the rate of the reaction is gi"en by rrhenius la$, $hich is the main explana-
tory target of absolute reaction rate theory. It $as de"eloped in *::. 'the
article appeared in English translation in 7ac! 8 >aidler *.-2+ and defines
the rate constant -@

-C2 exp'-E
2
?30+
expressing the rate constant for a chemical reaction in terms of a frequency
factor 2 and an acti"ation energy E
2
.
rrhenius concept of acti"e cane sugar contains three important com-
ponents of the theory of reaction rates, $hich can be reconstructed as the
follo$ing set of claims@
* #here is some acti"e component of the reactants in"ol"ed in the reac-
tion, $ithout $hich the reaction $ould not occur.
( #he acti"e and inacti"e components are in equilibrium.
; #he acti"e form of the reactants is continuously remo"ed by the reac-
tion.
1onditions *-; are, in generalized form, the basic assumptions of all reac-
tion rate theories.
rrhenius la$ posed the question of ho$ to account for both the fre-
quency factor and the acti"ation energy, and, as described in >aidler 8 4ing
*.:;, a number of candidate theories appeared.
In the ,ollision theory the frequency factor 2 in rrhenius equation is
interpreted as equal to the frequency of collisions 4 bet$een the reactants.
#he collision theory assumes that all the reactants are hard spheres, and that
any collision that has sufficient energy to reach the acti"ated state $ill pro-
ceed to complete the reaction.
modified collision theory often introduces a probability factor P
$hich measures the probability that a collision $ill lead to a completed chem-
ical reaction. Hence, in the modified collision theory@
-CP4 exp'-E
2
?30+
*/) Hinne Hettema
#he fudge factor P is introduced since the collisional cross section of a mol-
ecule bears no clear relationship to the probability for a chemical reaction.
%hile the collision theory $or!s $ell for reactions bet$een mono-atomic
gases, it brea!s do$n for reactions bet$een more complex molecules. In this
respect, the collision theory is not capable of clarifying the internal mecha-
nisms of chemical reactions in the necessary detail.
nother candidate is the thermo+ynami, formulation, in $hich the reac-
tion rate constant is expressed in thermodynamic quantities as
k=
kT
h
K
t

=ince the equilibrium bet$een the acti"ated state and the reactants is a nor-
mal chemical equilibrium, the equilibrium constant 5 can be related to the
thermodynamic theory of chemical reactions, and hence, it can be related to
the normal thermodynamic concepts of free energy, enthalpy 'heat con-
tent+, entropy, and so forth. #his yields a measure of the entropy changes
associated $ith the reaction.
(.* bsolute reaction rate theory
bsolute reaction rate theory is a theory that aims to pro"ide explanations
for both the acti"ation energy and the pre-exponential factor 'the fre-
quency factor+ in the rate equation from first principles. Its underlying theo-
ries are quantum mechanics and statistical mechanics. #he success of the the-
ory depends on an accurate calculation of the potential energy surface of the
reaction, as $ell as a detailed consideration of the initial and final states of the
molecules.
#he theory also introduces a precise concept of a transition state $hich is
li!e a normal molecule. #he transition state has a definite structure, mass,
and so forth. #he only exception is that there is one particular direction of
motion 'the reaction coordinate+ $hich causes the molecule to brea! up
into the end products of the reaction.
#he situation is s!etched in 0igure *. Dn the right is a channel of reac-
tants $hich transforms along a reaction coordinate into a channel of prod-
ucts. t the height of the energetic barrier bet$een the reactants and the
products lies the transition state, $hich is thus specified as a particular type
of molecule, $ith the structural property that there is one particular internal
coordinate $hich leads to a decomposition of the molecule.
#he further de"elopment of absolute reaction rate theory is based on the
statistical mechanics of the equilibrium bet$een the reactants and the transi-
tion state. Eyrings introduction of statistical mechanics into the expression
of the rate equation is based on the idea that the potential energy surface can
0he 1nity of Chemistry an+ Physi,s */*
be calculated $ith quantum mechanics, and the motion of the nuclear frame
can subsequently be treated classically $ith statistical mechanics.

0igure *@ #he potential energy surface for a three-atom reac-
tion, indicating the reaction coordinate and the transition state
at the saddle point.
It is therefore clear that the absolute theory of reaction rates requires accu-
rate calculations of the potential energy surface for the reaction. =uch precise
calculations $ere not possible in the *.;)s, and hence Eyring de"eloped a
semi-empirical form of quantum mechanics that gi"es access to the potential
energy surface $ith sufficient precision to allo$ predictions from the theory.
Eyrings formulation of absolute reaction rate theory uses the follo$ing
assumptions@
E* #he potential energy surfaces can be calculated $ith quantum mechan-
ics 'or a semi-empirical form of quantum mechanics+.
E( #he beha"ior of the nuclear frame on the potential energy surface
'note that this therefore includes the 7orn-Dppenheimer approxima-
tion+ can be described $ith statistical mechanics.
E; #he decomposition of the transition state into the reactants can be de-
scribed as a translational motion along the reaction coordinate.
>et us reconstruct the remainder of the argument in the form in $hich it is
gi"en in Alasstone et al. *.,*. #he !ey element of statistical mechanics is the
partition function '4ustan+ssumme+ 4@
*/( Hinne Hettema
z=g
i
exp
(
e
i
kT
)

$here )
i
is the degeneracy of the state corresponding to energy e
i
. #he com-
plete partition function for any system is complex to calculate, since it in-
"ol"es all electronic, translational, "ibrational and rotational motions of the
system $ith their degeneracies and corresponding energy le"els. #he rate
formula of the absolute theory of reaction rates is gi"en in terms of the parti-
tion functions of the reactants and the transition state by
k=
kT
h
Z

Z
A
Z
B
Z . ..
exp
(
E

0
RT
)

#he ad"antage of this formulation is that the partition functions for all com-
pounds featuring in the reaction '4
2
, 4
6
, et,.+ can be calculated using statisti-
cal mechanics for "ibrational and rotational motion of mechanical systems.
%hile this is still a difficult problem, a detailed consideration of different re-
acting systems yields a mechanistic insight in ho$ the reaction occurs on a
molecular le"el. 0igure ( presents a s!etch of the situation.

0igure (@ #he potential energy surface for reaction seen along
the reaction coordinate. #he parabolic cur"es $ith energetic
le"els in them should be read as being perpendicular to the re-
action coordinate.
(.( %igners three threes
detailed summary of absolute reaction rate theory $as gi"en in %igners
'*.;:+ presentation at the *.;2 0araday conference '>aidler 8 4ing *.:;
contains a brief discussion of this conference and the role it played in the
0he 1nity of Chemistry an+ Physi,s */;
subsequent adoption of the theory+, $here he summarized the challenges,
types of reactions, and assumptions of the theory as a set of three threes.
#hese are presented in #able * and translated into a specific set of steps
'%=+, groups '%A+ and assumptions '%+.

#able *@ %igners three threes that characterize transition state theory 'after
9iller *..:+.
Three steps in the theory of kinetics
%=* 5etermine potential energy surfaces
%=( 5etermine elementary reaction rates
%=; =ol"e rate equations for complex reaction mechanism
Three groups of elementary reactions
%A* Eibrationally?rotationally inelastic collisions 'not a chemical reaction+
%A( 3eacti"e collisions on a single potential energy surface
%A; Electronically non-adiabatic reacti"e collisions
Three assumptions
%* Electronic adiabaticity@ the electronic configuration is in the lo$est quantum
state for each configuration of the nuclei
%( #he "alidity of classical mechanics for the nuclear motion
%; Existence of a di"iding surface that tra6ectories do not re-cross

%igner referred to the theory in this paper as #he #ransition =tate 9ethod
and distinguished three steps. %=*@ #he determination of potential energy
surfaces, $hich gi"es Fthe beha"iour of all molecules present in the system
during the reaction, ho$ they $ill mo"e, and $hich products they $ill yield
$hen colliding $ith definite "elocities, et,.G '%igner *.;:, p. (.+. #he solu-
tion of this problem requires the calculation of a potential energy surface,
$hich is a quantum chemistry problem. %=(@ #he next step is the calculation
of elementary reaction rates. %=;@ #he third problem is to combine these
elementary reactions into a series of reactions $hich ma!e up the o"erall
chemical transformation. Df these, the elementary form of reaction rate
theory only considers %=* and %=( and ignores %=;.
%igner classified the elementary reactions in three groups@ inelastic colli-
sions, in $hich the molecules exchange "ibrational and?or rotational energy
but do not change their chemical composition, reactions on a single potential
energy surface $hich in"ol"e no change in electronic quantum numbers, and
reactions in"ol"ing multiple potential energy surfaces 'non-adiabatic reac-
tions+. Dnly the second type of elementary reactions can be treated $ith
transition state theory, hence, only %A( is considered in the theory. 0inally,
%igner discussed three assumptions. #he first one is the adiabatic assump-
tion '%*+, $hich assumes that during the reaction the molecular system
stays on the lo$est possible potential energy surface and there is no change
of electronic configuration. #he second assumption is that the motion of the
*/, Hinne Hettema
nuclei can be described $ith classical mechanics '%(+. #he third assump-
tion requires that the reaction does not go bac!$ards, i.e. all systems cross-
ing the barrier are reacting systems '%;+. #he consequence of this is that
the step from the reactants to the transition state is the rate determining step
for the equation. Dnce a set of reactants form a transition state, this transi-
tion state $ill fall apart to form the end products of the reaction. #herefore,
%; adds additional precision to the specification of the transition state.
#he three threes form a more elaborate formulation of the Eyring condi-
tions 'E*-E;+ in the sense that they add precision and in this $ay also indi-
cate directions for future research 'e.). reactions on non-adiabatic surfaces,
quantum effects in nuclear motion, et,.+.
(.; =ummary
#he structure of absolute reaction rate theory is gi"en in 0igure ;. #he pur-
pose of the theory $as to pro"ide exact expressions for the t$o "alues E and
2. 0rom the "ie$point of quantitati"e explanations for these quantities the
theory has been moderately successful, but has, in the $ords of >aidler and
4ing '*.:;+, Fits difficultiesG.

0igure ;@ #he conceptual structure of the absolute reaction rate
theory and its comparisons to the thermodynamic theory and
collision theory. #he arro$s indicate structural relationships be-
t$een the theories.
Historically the theory $as not immediately accepted upon its appearance.
s is seen in the proceedings of the -2
th
general discussion of the 0araday
=ociety '$hich $as held at the Hni"ersity of 9anchester, *;-*/ =eptember
*.;2+, there $ere some $ho sa$ the theory as some$hat speculati"e.
Ho$e"er, the most interesting aspect of the absolute reaction rate theory
is that it pro"ided a
IJK conceptual frame$or! $ith the aid of $hich experimental chemists 'and
others+ can gain some insight into ho$ chemical processes occur. Dn this
score the theory must recei"e the highest mar!sL for nearly half a century it
has been a "aluable $or!ing tool for those $ho are not concerned $ith the
0he 1nity of Chemistry an+ Physi,s *//
calculation of absolute rates but are helped by gaining some insight into chem-
ical and physical processes. #he theory pro"ides both a statistical-mechanical
and a thermodynamic insight M one can ta!e ones choice or use both formula-
tions. I>aidler 8 4ing *.:;, p. (--,K
#hus, in the final analysis, the achie"ement of the theory $as primarily con-
ceptual@ it pro"ided "aluable insights into the mechanisms that dri"e chemical
reactions at a molecular le"el. Hence, the absolute theory of reaction rates is a
"ery strong example for the unity of science M it is precisely one of those ex-
amples $here it is hard to imagine chemistry $ithout physics, but at the same
time it is a chemical theory in that it focuses on molecules, molecular struc-
tures, and transformations.
#he remainder of this paper $ill be concerned $ith ho$ the absolute the-
ory of reaction rates fits philosophical conceptions of the unity of science.
0rom the "ie$point of reduction and unity of science, the theory has a num-
ber of unique features@
*. #he introduction and specification of the transition state in terms of a
specific location on the potential energy surface of the reaction and its
characterization as a molecule $ith specific propertiesL
(. #he degree to $hich explanation depends on ,omparison bet$een the
collision, thermodynamic, and quantum mechanical?statistical me-
chanical formulations of molecular quantities.
If it is the case that the unity of science is the end product of some process of
theory reduction, then this case should fit a reducti"e model. =imilarly, if the
unity of science is not based on a reducti"e model, there should be a fit $ith
one of the non-reducti"e proposals.
In the next section it is my aim to discuss some approaches to the topic of
reduction before returning to the question ho$ the theory of absolute reac-
tion rates might fit a reducti"e model and $hat the consequences of such a fit
might be.
;. #he unity of science@ reducti"e, non-reducti"e, and
naturalized approaches
In this section, it is my aim to present the &agelian approach to reduction as
a close reading of the form in $hich it $as originally gi"en by &agel '*.-*+,
as $ell as to outline some aspects of the recent interpretation of &agels the-
ory. I then discuss a number of non-reducti"e approaches, and conclude $ith
a proposal for a naturalized &agelian reduction model that combines im-
portant aspects of a defensible &agelian model $ith non-reducti"e approach-
es, and $hich is adaptable to interesting cases of scientific explanation. #he
*/- Hinne Hettema
!ey concept of naturalized &agelian reduction is that the philosophical no-
tion of reduction should be a paraphrase, in some formal language, of $hat
happens $hen scientists claim that one theory explains another. #he concept
is discussed in more detail in =ection ;.;.
;.* &agelian 3eduction
&agels formal requirements for reduction are $ell !no$n and are generally
ta!en to be the requirements of connectibility and deri"ability, stating that a
linguistic connection bet$een the languages of the reduced and reducing the-
ory has to exist, and that the reduced theory has to be deri"able from the re-
ducing theory ,um reduction postulates. Df the formal conditions, especial-
ly the notion of connectibility requires further consideration.
#o begin $ith, the reduced and reducing sciences usually ha"e a number
of terms in common '&agel *.-*, p. ;/*-(+. %hile the meaning of these
terms is fixed by procedures internal to both sciences, the meanings of terms
of a certain common "ocabulary $ill coincide sufficiently to pose no further
problems for deri"ability. Dn the other hand, there is also a class of terms
$hich occur in the reduced science but not in the reducing one. Hence, de-
ri"ability can only be achie"ed $hen the concepts nati"e to the reduced sci-
ence can be explicated in terms of the reducing one.
#o achie"e connectibility, &agel introduced, in addition to the formal
requirements, the notion of coordinating definitions 'here called reduction
postulates+ as an additional assumption. #he reduction postulates modifies
the reducing science to o"ercome the issue that, as &agel states, deri"ation is
impossible if the premise of the argument 'i.e. the reducing science+ does not
already contain the necessary concepts of the reduced science. Hence, the
reducing science has to state, in some meaningful sense, $hat the concepts of
the reduced science are. #he reduction postulates stipulate
suitable relations bet$een $hate"er is signified by and traits represented
by the theoretical terms already present in the primary science Ii*i+., pp. ;/;-
,K.
%hile the role of the reduction postulates is simple enough, the exact formu-
lation of the reduction postulates themsel"es is far from simple. 0or instance,
&agel discussed three possible !inds of lin!ages postulated by reduction pos-
tulates 'i*i+.+, $hich can be paraphrased as follo$s@
*. #he lin!s are logical connections, such that the meaning of 2 as fixed
by the rules or habits of usage is explicable in terms of the established
meanings of the theoretical primiti"es in the primary discipline.
(. #he lin!s are con"entions or coordinating definitions, created by de-
liberate fiat, $hich assigns a meaning to the term 2 in terms of the
0he 1nity of Chemistry an+ Physi,s */2
primary science, sub6ect to a criterion of consistency $ith other as-
signments.
;. #he lin!s are factual or material, or physical hypotheses, and assert
that existence of a state 6 in the primary science is a sufficient 'or
necessary and sufficient+ condition for the state of affairs designated
by 2. In this scenario, the meanings of 2 and 6 are not related ana-
lytically.
It is thus important to realize that &agels criteria for reduction postulates
are open to a number of interpretations, and can be instantiated in actual
practice in a number of $ays. =pecifically, as also 4lein '()).+ has argued, the
reduction postulates refer to the representational po$er of the reducing the-
oryL its ability to introduce the terms present in the reduced science. &ote
that &agels second formal requirement states that the terms are fixed by
meanings and use local to the rele"ant theory and hence this sort of represen-
tational po$er is not a tri"ial requirement.
#he &agelian deri"ability condition states@
IJK a reduction is effected $hen the experimental la$s of the secondary sci-
ence 'and if it has an adequate theory, its theory as $ell+ are sho$n to be the
logical consequences of the theoretical assumptions 'inclusi"e of the coordi-
nating definitions+ of the primary science. I&agel *.-*, p. ;/(K
In addition to the formal requirements, &agel specified a number of informal
requirements. #hese introduce many qualifications and conditions that $ill
pro"e to be rele"ant in $hat follo$s. 9oreo"er, the informal requirements
contain many qualifications to the reduction scheme that are commonly
o"erloo!ed.
#he main reason for introducing the informal requirements is that the
formal requirements are, by themsel"es, incapable of distinguishing bet$een
$orth$hile and $orthless theory reductions. s &agel noted, the formal
conditions could in many cases be satisfied rather tri"ially $ith some a+ ho,
assumptions. #he informal conditions are there to bloc! this sort of tri"ial
reduction.
#he first informal requirement is that of 'external+ corroboration of the
reducing theory. #hat helps in the unification of the sciences by expanding
their domains of applicability, and strengthens the case for the corroboration
of the reducing theory.
#he second informal requirement is that of maturity of the reducing theo-
ry. s &agel notes, the ideal gas la$ could be reduced to the !inetic theory of
gases only after the formulation of 7oltzmanns statistical interpretation of
the second la$ of thermodynamics, and similarly the reduction needs a suffi-
ciently mature mechanics to be counted as a success.
<erhaps the most important requirement for the further discussion of the
reduction of chemistry to physics, and one often o"erloo!ed in this context,
*/: Hinne Hettema
is the third one. &agel claimed that it is frequently a mista!e to assume that
reduction amounts to the deri"ation of the properties of one sub6ect matter
from the properties of another, and therefore denies that the reduced science
can be eliminated on the basis of such property reduction, and that, in fact,
Fthe conception of reduction as the deduction of properties from other prop-
erties is potentially misleading and generates spurious problemsG 'i*i+., p.
;-,+. Instead, &agel argued that the "arious properties ascribed to chemical
elements, for instance, are the end result of theories about chemical elements.
If such theories are later sho$n to be reducible to theories of atomic physics,
then this pro"es the existence of a logical relationship bet$een theories, but
does not pro"ide an argument for the reduction of the essential natures of
the concepts that function in these theories.
It is thus important to note that &agel did not defend a form of reduc-
tionism that allo$s for a nothing but approach to reduction. =pecifically, he
did not defend a "ie$ $here for instance an atom can be said to be nothing
but a collection of a nucleus $ith a certain number of electrons. %hile it is
formally required to ma!e such a statement in order for the reducing theory
to be able to say something about atoms in the first place, the requirement is
a formal and not an ontological one.
#his is an important point precisely because this third informal require-
ment establishes the ontological independence of the reduced science@ in
many cases of reduction, the existence of reduction is a matter of the exist-
ence of a logical or formal relationship bet$een the reduced theory and the
reducing theory ,um the reduction postulates, $here the latter allo$ a formal
deri"ation relationship but do no ontologically hea"y lifting.
<hilosophers of science ha"e tended to focus on the formal requirements
o"er the informal requirements, and argued that the connectibility require-
ments 'or reduction postulates+ specify ontological identities. #he notion
that reduction postulates ha"e to represent identities $as most strongly de-
fended by 1ausey '*.22+. He analyzed sentences of the form@
x@ x x
and noted that, $hen $e ha"e a true sentence of this form, it could be either
one of three cases 'i+ and are accidentally co-extensional, 'ii+ and are
nomologically correlated 'and co-extensional+, or 'iii+ and are are identi-
cal. Dn 1auseys analysis, 'i+ can be ignored, $hile 'ii+ is question begging as
a reduction sentence and only 'iii+ leads to an acceptable reduction sentence.
s he noted $ith regard to 'ii+, the concept of an 11= 'ttribute 1orrela-
tion 1onnection =entence+@
7y no$ it should be fairly clear that IJK mere attribute-correlation la$ sen-
tences, are not acceptable as connecting sentences. 11=s are mysterious,
causal la$-sentences that are themsel"es in need of explanation. If they are
0he 1nity of Chemistry an+ Physi,s */.
used as connecting sentences IJK then $e do not explain #( in terms of the
la$s of #* but rather in terms of #* plus these mysterious correlation la$s.
II*i+., p. :-K
Hence 1ausey concluded that adequate correlations of the form '2+ require
Fthing-identitiesG and Fattribute identitiesG 'i*i+., p. 2.+.
3ecently, the pendulum on &agelian reduction has s$ung the other $ay.
4lein '()).+ and "an 3iel '()**+ ha"e argued that &agelian reduction should
not be read as a defense of ontological reductionism. 4lein argues that
&agels condition of connectibility focuses on the degree to $hich the reduc-
ing theory can represent notions of the reducing theory. =imilarly, "an 3iel
argues that the $ay in $hich &agels frame$or! for reduction is commonly
read does not correctly represent the careful remar!s about the inter-
theoretic relationships that accompanied it.
5izad6i-7ahmani, 0rigg 8 Hartmann '()*)+ argue that a generalized
&agel-=chaffner model, in $hich the reduction postulates are factual claims,
is ali"e and $ell. n o"er"ie$ of their proposal is presented in 0igure ,.
#hey defend the generalized &agel-=chaffner model against se"en specific
ob6ections, concluding that none of them apply. In their terminology, the
generalized &agel-=chaffner model consists of a theory 0
P
reducing to a the-
ory 0
7
through the follo$ing steps@
*. #he theory 0
7
is applied to a system and supplied $ith a number of
auxiliary assumptions, $hich are typically idealizations and boundary
conditions.
(. =ubsequently, the terms in the specialized theory 0
8
7
are replaced $ith
their correspondents "ia bridge la$s, generating a theory 0
8
P
.
;. successful reduction requires that the la$s of 0
8
P
are appro.imately
the same as the la$s of the reduced theory 0
P
and hence bet$een 0
8
P

and 0
P
there exists an analo)y relation.

0igure ,@ D"er"ie$ of the generalized &agel-=chaffner reduc-
tion proposed by 5iza6e et al. ()*).
=pecifically, t$o features of the generalized &agel-=chaffner model are $orth
noting. #he first one is that in this model the reduction postulates are part of
the reducing theory, rather than some auxiliary statements that ha"e a pri-
marily metaphysical import. =pecifically, 5izad6i-7ahmani et al. argue that of
the three types of lin!ages that may be expressed by reduction postulates, the
first t$o can be discarded and reduction postulates express matters of fact.
#his is so, because the aim of scientific explanation is neither Fmetaphysical
*-) Hinne Hettema
parsimonyG nor Fthe defense of physicalismG 'i*i+., p. ,)/+. #hey argue for a
naturalized reading of &agel, in $hich the aim of reduction is consistency
bet$een the reduced and reducing theory, and confirmation of 0
P
entails
confirmation of 0
7
for domains $here there is significant o"erlap.
In this manner, 5izad6i-7ahmani et al. claim that reductions ha"e a high
li!elihood of occurring in situations, such as the present case of the unity
bet$een chemistry and physics, $here theories ha"e an o"erlapping target
domain@
%e are committed to the claim that if $e ha"e a situation of the !ind de-
scribed abo"e 'in $hich the t$o theories ha"e an o"erlapping target domain+,
then one must ha"e a reduction. II*i+., p. ,*)K
;.( &on-reducti"e approaches to the unity of science
In this section, I $ill discuss some of the non-reducti"e approaches that may
assist in understanding and characterizing the relationship bet$een theories
of physics and theories of chemistry. #he examples are 5arden and 9aulls
notion of an interfield theory, and "arious approaches to accommodation
and structural similarity. I $ill not focus on non-reducti"e theories, such as
the approach by 5uprN '*..;+, $hich ad"ocate disunity.
#he first model $e $ill consider is that of interdisciplinarity. #he prom-
ise of the interdisciplinarity or interfield theory approach is that it can pro-
"ide a non-reducti"e model for the unity of science, in $hich both chemistry
and physics play an equal part in the relationship.
Dne of the theories proposed to this end is the concept of an inter-field
theory proposed by 5arden 8 9aull '*.22+. #he notion of a field is basic
to the model. field is characterized 'along the lines de"eloped in =hapere
*.22+ as based on an ordered domain of phenomena, to $hich it introduces
a specific set of practices and techniques, perhaps $ith some local theories@
>ocal theories that are specific to a field are called intrafield theories. 0ields
and intrafield theories cannot be equated. =e"eral, sometimes competing, theo-
ries are possible@ field at one point in time may not contain a theory, or may
consist of se"eral competing theories, or may ha"e one rather successful theo-
ry. I5arden 8 9aull *.22, p. ,:K
In this manner, fields are not competing in the same $ay as theories, and it is
also not possible to say that one field may reduce another@ the necessary
'&agelian+ relationships for theory reduction cannot obtain bet$een fields.
Interfield theories are specific theories $hich use concepts and data from
neighboring fields. #he definition of an interfield theory is a theory that does
some or all of the follo$ing 'i*i+., p. /.+@
0he 1nity of Chemistry an+ Physi,s *-*
*. #o sol"e 'perhaps correctly+ the theoretical problem $hich led to its gen-
eration, that is, to introduce a ne$ idea as to the nature of the relations be-
t$een fieldsL
(. #o ans$er questions $hich, although they arise $ithin a field, cannot be
ans$ered using the concepts and techniques of that field aloneL
;. #o focus attention on pre"iously neglected items of the domains of one or
both fieldsL
,. #o predict ne$ items for the domains of one or both fieldsL
/. #o generate ne$ lines of research $hich may, in turn, lead to another in-
terfield theory.
Oet it is hard to see that the interfield concept $ould be incompatible $ith a
local "ersion of the naturalized &agelian reduction $e de"eloped in the pre-
"ious section. 0ields can be populated by theories, and reduction relation-
ships in a &agelian sense may exist bet$een theories in different fields. In
this regard it is especially $orth noting that the reading of the reduction pos-
tulates as matters of fact plays the role of establishing the interfield theory
to a significant degree.
In a recent paper, Harris '()):+ has argued that the early theories of the
chemical bond are best concei"ed as an interdisciplinary entity, $hich dra$s
equally on physics and chemistry. ccording to Harris, the hallmar! of this
interdisciplinary entity is the cooperation bet$een chemists and physicists on
problems of common interest@
IJK physics and chemistry $ere disco"ering problems of collaborati"e "alue
$ithin a common theoretical frame$or!. #here is no a"oiding the fact that un-
til physical methods $ere a"ailable to chemists, there $as no real possibility of
disco"ering the mechanism of bonding. IHarris ()):, p. ::K
Harris argues that from this perspecti"e, the claim that chemistry $as re-
duced to physics has to be re"ised, since the assumption that a successful re-
duction $as the prime consequence of this interdisciplinarity does not
properly assess the historical facts and the "alue of the interdisciplinarity to
both physicists and chemists. Harris argument is primarily historic. =he con-
trasts the interdisciplinary relationship $ith a reducti"e relationship $hich
she does not flesh out in a lot of detail but describes in terms of an attempted
ta!eo"er, quoting 7orn $here he expressed Fa belief that the "ast territory of
chemistry $as not only important for physicists to explore, but that this
$or! $as necessary in order for physicists to impose her la$s upon her sister
scienceG '7orn as quoted in i*i+., p. :*+.
3ecently, there has also been rene$ed interest in the &eurathian program
for the unity of science. #he program $as discussed by 1art$right et al.
'*..-+ and <otochni! '()**+ in the context of the unity of science. &eu-
raths $or! is easily accessible in 1ohen 8 &eurath *.:;. He "ie$ed the uni-
ty of science as part of a broader encyclopedic program that $as also educa-
*-( Hinne Hettema
tional in character. characteristic of &euraths concept of the unity of sci-
ence is that it has room for multiple explanations for a single phenomenon.
&eurathian unity of science is closely lin!ed to 5uhemian holism, in the
sense that hypotheses are tested in a holistic manner, against a unified $hole
of theoretical statements.
In this context, it is interesting to note that =pector '*.2:+ has ad"anced
claims "ery similar to those of Harris to argue precisely that the relationship
is one of reduction, in fact, an entire branch reduction of chemistry to phys-
ics $hich seems to dra$ into question the notion of non-reducibility, as $ell
as that of a further specification of the reduction relation in question.
In practice, the encyclopedic approach builds on $hat the initial sciences
ha"e to offer, and then starts loo!ing at the sort of relationships that might
hold bet$een them. In his *.;2 essay #he 5epartmentalization of Hnified
=cience, &eurath described the follo$ing approach to unification@
If one starts $ith a great many special disciplines IJK o"erlapping one anoth-
er, one might axiomatize all groups of statements ready for it. Dne might se-
lect all cases in $hich the logical structure of a group of statements is identical
$ith the logical structure of another group. I&eurath *.:;a, p. ()(K
&eurath called this approach to the unity of science encyclopedism and
contrasted it to pyramidism. He "ie$ed the latter as inspired by metaphysi-
cal "ie$s on the unity of science, in $hich@
&ot a fe$ classifications and arrangements of the sciences can be regarded as
deri"ates from the architectonic structure of such metaphysics, e"en if their
creators $ere interested in empiricism. II*i+., p. ();K
=uch a metaphysical commitment is a bad idea according to &eurath. Hence,
the unity of science is not based on a hierarchical structure of nature, but ra-
ther on an encyclopedic model, in $hich one is
IJK satisfied $ith a rough bibliographic order for an initial orientations, made
by librarians. IDneK accepts the fact that the "ast mass of the groups of state-
ments are, as it $ere, in one place. 1ertain coherent forms could be arri"ed at
by means of axiomatization or other procedures and a complicated net$or!
gradually createdL there is no symmetrically pyramidical edifice. II*i+., p. (),K
&euraths model is thus best characterized as anti-reductionist@ the holistic
criterion for acceptance of statements is $hether they fit $ith an existing
$hole, and once constructed, many $holes might structurally connect $ith
each other. In this $ay, &eurath allo$ed se"eral competing explanatory sys-
tems to co-exist, and argued that some systems are better suited to pro"ide
explanations in gi"en situations.
0he 1nity of Chemistry an+ Physi,s *-;
lisa 7o!ulich '()):+, in a study of the relationship bet$een classical and
quantum mechanics, de"elops a notion of 'non-reducti"e+ interstructural-
ism@
Interstructuralism is an approach to inter-theory relations that emphasizes the
importance of structural continuities and correspondences in gi"ing an ade-
quate account of the relation bet$een t$o theories. It recognizes a richer di-
"ersity of correspondence relations than does any form of reductionism or
pluralism. I7o!ulich ()):, p. *2;K
7o!ulich claim concerns specifically +ynami,al structures. 0rom this per-
specti"e, she argues that there may be some question as to ho$ this model
$ould apply to different theory pairs, though she does mention chemistry as
a potential candidate for such a relationship 'i*i+., p. *2;+. =he presents in-
terstructuralism as a middle path bet$een reductionism and theoretical plu-
ralism, $hich ta!es important lessons from either approach.
Especially, she argues that interstructuralism lea"es the higher le"el theo-
ries 'the reduced theories in a reduction relationship+ intact as explanatory
theoretical entities in their o$n right. Ho$e"er, from reductionism she ta!es
the idea that the domains of phenomena are not entirely distinct, and that in
this sense, an o"erall theory of ho$ these phenomena are related is bound to
lead to ne$ insights.
#o the degree that 7o!ulich identifies reductionism $ith the strict inter-
pretation of &agelian reduction as identities ,um strict deri"ation 'and her
boo! suggests that she does+ the approach I am ad"ocating to &agelian re-
duction is to a significant degree compatible $ith interstructuralism.
;.; &aturalized reduction
In this paper, my proposal is to de"elop and defend a naturali9e+ &agelian
reduction, $hich ta!es the &agelian model as a heuristi, model to inter-
theory relationships in actual science. 1andidate theories for the naturalized
&agelian reduction are those theories $hich claim e.planations of 'aspects+
of one theory by another.
&aturalized &agelian approach then proceeds along the follo$ing lines@
*. 0irst $e see! out cases of claimed explanations in actual science.
(. %e then proceed to rationally reconstruct these cases of explanations.
;. =ubsequently, $e see! to formulate a paraphrase of this rational recon-
struction in terms of a 'more or less formal+ specification of both the
basic assumptions and unique features of the explanation.
,. =ubsequently, $e establish the necessary lin!ages $hich ma!e the ex-
planation $or!.
/. >astly, $e e"aluate the formal structure in terms of either a reducti"e
or suitable non-reducti"e model of the unity of science.
*-, Hinne Hettema
#he main reason for ad"ocating a naturalized conception of the &agelian
reduction as the correct relation of unity bet$een chemistry and physics is
that this seems to be one of the fe$ conceptions of this relationship that is
capable of dealing $ith the conceptual strength of chemical language.
It is by no$ $ell established in the philosophy of chemistry that the rela-
tionships bet$een theories of chemistry and theories of physics do not fit the
requirements of the &agelian reduction model $hen it is read in terms of
identities ,um strict deri"ation. s the naturalized &agelian reduction con-
tends, it is explicitly non-eliminati"eL rather, &agelian reduction aims to be a
'logical+ paraphrase of $hat exactly happens $hen one theory explains an-
other.
#he percei"ed disunity of the language of chemistry and physics is to a
large degree responsible for the some$hat unfortunate introduction of the
concept of ontological reduction in the philosophy of chemistry, a blan!
cheque $ritten to metaphysics in payment for the percei"ed failure of &age-
lian reduction. It is the aim of naturalized &agelian reduction to bounce that
cheque, and reclaim room for theoretical explanation $ith ontological inde-
pendence.
s stated in the introduction, my treatment of these issues in the present
paper is mostly informal in order to bring out the approach. I ha"e proposed
a formal frame$or! for naturalized reduction $hich is based on the structur-
alist approach to scientific theories in Hettema '()*(+.
,. bsolute reaction rates as a case study for natural-
ized reduction
In this section I consider absolute reaction rate theory as a case study for
naturalized &agelian reduction. #he rational reconstruction required for our
discussion is largely found in =ection (. #he main aim of this section $ill be
to discuss the structure of the theoretical frame$or! and the lin!ages be-
t$een the rele"ant components of the net$or!. #he sort of unity of science
that is supported by the consideration of the absolute reaction rate theory is
discussed in the next section.
#he characterization of the lin!ages $ill in"ol"e a number of steps. #he
first step is the specification of the &agelian connections bet$een the theo-
ries that constitute the net$or! of explanation. 0rom these, I $ill dra$ t$o
main conclusions $hich allo$ us to characterize the uniqueness of absolute
reaction rate theory as a proposed case of reduction@ in the first place, I argue
that some elements of this theory remain unconnected, and hence are unique
features of the theory, and secondly, the &agelian connections, $hen read as
0he 1nity of Chemistry an+ Physi,s *-/
statements of fact, allo$ us to specify the unique role played by comparison
in the theory. #he last step is the e"aluation of the theory as a case study in
naturalized &agelian reduction. #his $ill assist in further specifying some of
the necessary detail of naturalized &agelian reduction.
s I $ill argue in this section, the theory of absolute reaction rates exhib-
its a number of interesting features $hich pro"e to be unique features of the
theory. #hese are a specification of the transition state and the degree to
$hich the comparison of the three different approaches M statistical mechan-
ics, collision theory, and thermodynamics M pro"ides further insight into the
calculation of the quantities 2 and E
2
. #he combination of these t$o unique
features gi"es rise to a third@ the fact that in the absolute reaction rate theory
multiple theories cooperate in the explanation. #he role played by these
unique features of the theory is specified in detail by the specification of the
&agelian connections.
,.* 3eduction bet$een theories@ &agelian connections and deri-
"ations
#he first step in the naturalized reduction program is to formally paraphrase
the reduction of the rrhenius equation by the "arious theories that consti-
tute the net of absolute reaction rate theory. s $e ha"e seen in the pre"ious
discussion, the theory needs to explain the pre-exponential 'or frequency+
factor 2 and the acti"ation energy E
2
. #he formal paraphrase of explanation
in terms of reduction is &agels formal conditions of ,onne,ti*ility and +eri/&
a*ility. s $as already indicated in the preceding sections, the contention of
naturalized &agelian reduction is that, of these conditions, connectibility
does a significant amount of scientific $or!, $hile deri"ability is a relati"ely
pedestrian affair.
$.1.1 2,ti/ation ener)y
#he acti"ation energy may be identified $ith the difference in energy be-
t$een the ground state of the reactants and the point on the potential energy
surface $hich corresponds to the transition state M a molecular structure
$hich can be specified $ith sufficient precision to allo$ its exact calculation
'though $ithin the limits of quantum chemical methods and approximations
such as the 7orn-Dppenheimer approximation+. Hence $e ha"e, I belie"e, a
relati"ely non-contentious case for i+entifi,ation of the acti"ation energy,
under the condition that $e define a transition state in terms of its location
on the potential energy surface. #he real $or! of the reduction is, ho$e"er,
done precisely by this condition.
#he &agelian identification is thus a t$o-step process, $hich ta!es us
from 'i+ a stipulation of a transition state in terms of a structure located at a
*-- Hinne Hettema
particular location on the potential energy surface, to 'ii+ an i+entifi,ation of
the acti"ation energy in terms of the energy difference bet$een the ground
state and the transition state.
Eyrings theory is note$orthy for the amount of precision it allo$s in the
specification of the transition state at a molecular le"el. s $e ha"e seen, a
bac!ground postulate $hich has no counterpart in the rrhenius equation is
that the reaction may be "ie$ed as a translational motion along the reaction
coordinate. %hereas the transition state $as foreshado$ed in the $or! of
rrhenius in the postulate of the acti"e form of cane sugar, the absolute
theory of reaction rates is capable of explicating exactly $hat the transition
state is. In brief, its structural features are@
*. #he motion along the reaction coordinate can be treated as a free
translational motion.
(. #he transition state lies at the saddle point of the potential energy
surface of the reaction.
;. It is a normal molecule in all other rele"ant respects.
It is $orth$hile to in"estigate ho$ this specification of the transition state
relates to the basic assumptions of both rrhenius equation and absolute
reaction rate theory. It is particularly interesting in this context that the no-
tion of the transition state gains additional precision and is in particular by
Eyrings theory in terms of an
IJK ordinary molecule, processing all the usual thermodynamic properties,
$ith the exception that motion in one direction, i.e. along the reaction coordi-
nate, leads to decomposition at a definite rate. IAlasstone et al. *.,*, p. *)-**K
In terms of a &agelian model, it is thus not a case of straightfor$ard identi-
ties ,um deri"ation that leads to the specification of the acti"ated state. 3a-
ther, the reduction postulate for the acti"ation energy ta!es the form of a
statement of fact, one that has ta!en hard $or! in the reducing theory to ac-
complish.
#he fact that the reducing theory is transforme+ during the reduction is
generally recognized in discussions of &agelian reductions, as $e ha"e seen in
our discussion of the model of 5izad6i-7ahmani et al. '()*)+. In the present
case it may be argued, ho$e"er, that the specification of the transitions states
does more than mere a transformation of the reducing theory@ it interprets a
specific feature of the re+u,e+ theory in terms of the re+u,in) theory as a
concept that does not flo$ naturally from the reducing theory, and can only
be properly understood from the "ie$point of the reducing theory itself.
0urthermore, this specification relies on se"eral further theoretical con-
cepts@ the idea of a reaction as a translational motion along the reaction coor-
dinate, as $ell as a structural characterization of the acti"e complex as a par-
ticular type of molecule.
0he 1nity of Chemistry an+ Physi,s *-2
$.1. 0he Pre&e.ponential fa,tor
In the statistical formulation of the theory, the frequency factor is identi-
fied 'apart from the factor -0:h+ $ith a quotient of the partition functions of
the acti"ated state and the reactants. 7ut this identification is not the compel-
ling point of absolute reaction rate theory.
s in the case of the acti"ation energy, the real $or! is done by the sci-
ence itself. #he compelling point is that this identification allo$s for a
me,hanisti, insight into the dynamics of a chemical reaction. #he mechanism
for this mechanistic insight is the comparison of se"eral contending explana-
tory theories for the pre-exponential factor, $hich pro"ide mechanisms in
terms of intermolecular collisions or thermodynamic quantities.
#he mechanistic features are quite easy to see for the simple collision the-
ory. 7ut since the collision theory needs to introduce a fudge factor in the
form of a reacti"e probability P its predicti"e po$er is some$hat limited.
#he statistical mechanical theory fares better in this regard. %ith some sim-
plifying assumptions, it is possible to construct explicit partition functions in
terms of translational, rotational, and "ibrational motion for the reactants and
products, and hence gain significant insight into "arious types of reactions.
Indeed, a large part of the boo! by Alasstone, >aidler 8 Eyring '*.,*+ does
precisely that.
#he thermodynamic formulation of the reaction rate is another interest-
ing feature of the theory. #hermodynamic quantities are in general macro-
scopic quantities, and Eyrings thermodynamic formulation alongside the
statistical mechanical formulation of the theory allo$s for a specification of
thermodynamic energies and entropies of acti"ation in terms of a mechanical
model at the micro le"el.
#he interpretation of the partition function can be seen, along the lines of
=pectors '*.2:+ di"ision of labor bet$een the theoretical chemist and the
theoretical physicist, as falling $ithin the realm of Faccounting for the ar-
rangement and beha"ior of atoms and molecules IJK on the basis of current
physical theories regarding the structure of the atom and the la$s concerning
the beha"ior of its constituentsG 'e"en though =pectors final conclusion, that
this is e"entually done $ith quantum mechanics, is incorrect in this context+.
#he fact that $e can express 2 in terms of statistical mechanics or reinter-
pret it in terms of the collision theory forms an interesting 'and complicat-
ing+ feature of the classification of the present case as one of &agelian reduc-
tion. #hese re-interpretations form an important component of the attrac-
ti"eness of the theory, since they allo$ chemists to shift perspecti"e on the
theoretical model $here required, and cannot be ignored as a feature of re-
duction. It is in this context note$orthy that explanatory theories of $ea!er
strength, such as for instance the collision theory, are not discarded in the
explanation. Hence, the theory of absolute reaction rates forms a !ey exam-
*-: Hinne Hettema
ple of cooperation bet$een se"eral reducing theories, $hich turns the reduc-
tion relation from one bet$een t$o theories into an explanatory and compar-
ati"e relation on a net$or! of theories.
#he comparison of different approaches in the calculation of the pre-
exponential factor therefore has significant consequences for the philosophy
of science@ it establishes net;or- of reducing theories that can be e"aluated
on a criterion of explanatory strength. #he refinement and e"aluation of the
explanatory strength forms an important addition to the concept of &agelian
reduction, and moreo"er, is one that allo$s for disciplinary autonomy.
$.1.( 2 theory net ;ith lo,al re+u,tions
#he explanation of reaction rates thus proceeds in the context of a net of the-
ories, $hich is depicted in 0igure ;. %hile connecti"e and deri"ati"e lin!s of a
&agelian sort exist bet$een all these theoretical approaches, the reduction
cannot be summarized as a relationship bet$een t$o theories@ the strength of
the theory results from the detailed specification of the transition state $hich
ma!es the identification possible, and the comparison it allo$s bet$een the
different approaches.
Hence in the case of absolute reaction rate theory the explanation pro-
ceeds in terms of multiple underlying theories, $hich in turn can be e"aluated
and compared on the amount of reducti"e strength that they are capable of
pro"iding.
In this sense, the intertheory relationships bet$een chemistry and physics
require a net$or! of theories for their specification. #his has a number of
important consequences. In particular, it lends support to the characteriza-
tion of absolute reaction rate theory as an interfiel+ theory in the sense of
5arden 8 9aull '*.22+, $here the theories comprising the interfield are in
turn reducti"ely connected. In this context, it is crucial that the reduction
postulates carry limited, context-free information, so that the theoretical
context is lost $hile the reducti"e connection is made.
#his circumstance allo$s us to argue that, $hile the indi"idual theories
ma!e up the field, &agelian reduction relationships bet$een these indi"idual
theories do not in turn amount to tout ,ourt re+u,tion of the field. s is the
case in the reduction bet$een chemistry and physics, &agelian reduction
thus allo$s theoretical independence of the field.
In the concept of naturalized reduction I ha"e de"eloped, theoretical con-
cepts may be freely borro$ed from other fields, and reused as theoretical
patches in the de"elopment of further theories. =uch theoretical patching
in"ol"es a loss of context. s an aside, the loss of context that may accom-
pany intertheory reduction may formally be specified in terms of the chun!
and permeate approach to theories de"eloped for instance by 7ro$n 8 <riest
'()),, ()):+. #hey hold that such 'paraconsistent+ chun! and permeate
0he 1nity of Chemistry an+ Physi,s *-.
structures are e"en present in indi"idual theories. lternati"ely, these con-
cepts can also be logically de"eloped as part of a semantic or structuralist
model of theory nets and intertheoretic lin!s. 0or no$, $e $ill forgo these
formal specifications.
,.( #he unity of science@ reducing theories and disciplinary au-
tonomy
#he last step in my naturalized approach is e"aluating the reconstruction in
terms of a naturalized &agelian approach to the unity of science. Hp to this
point, I ha"e argued that considering the absolute reaction rate theory as a
case of naturalized &agelian reduction has gi"en us additional insight into the
structure and nature of the intertheory relationship that applies in this case.
%e no$ turn to the last step of the naturalized approach, $hich is the classi-
fication of the case study in terms of either a reducti"e 'or non-reducti"e+
model.
#he analysis of absolute reaction rate theory in terms of the naturalized
&agelian model has illuminated t$o unique features of the theory $hich are
of further interest for the philosophy of science. #hese are@
*. #he specification of the transition state as a uni<ue sort of mole,ule.
#his explicitly adds insights from the reduced theory to the reducing
theory.
(. #he comparison of se"eral potential reducing theories in terms of their
explanatory strength, $hich gi"es additional me,hanisti, insight into
the theory of chemical reaction rates.
reducti"e model $ill in the final analysis attempt to map these features into
the reducing theory. =uch a mapping is only possible after the explanation is
complete@ it is not possible to say a priori $hat the statistical mechanical or
thermodynamic features of the transition state are before the explanation of
the theory has been established, or to decide a priori $hich of the competing
reducing theories is the best fit.
In terms of a reducti"e model, therefore, the reducing theories and the
reduction postulates need to be read as a holistic $hole. #he specification of
the transition state in terms of a special !ind of molecule illustrates that the
reduction postulates in this case must be read as a case of representation in
$hich the reducing theory introduces a specific notion deri"ing from the re&
+u,e+ theory into the re+u,in) theory. #he specification of the transition
state in the present case cannot be read as a &agelian case of identification or
some form of extensional correlation if the conceptual patch made by the
reduced theory is ignored.
Dnce this conceptual patch has been imported into the reducing theory,
the notion of the transition state stands in an analo)y relationship to the r-
*2) Hinne Hettema
rhenius condition. s $e ha"e seen, 5izad6i-7ahmani et al. '()*)+ argue that
the specialization, application, and transformation that characterize their "er-
sion of &agelian reduction yields a final theory that stands in such an analogy
relation to the theory to be reduced. 0or the present case that implies that
the precise specification of the transition state $hich is furnished by absolute
reaction rate theory is analogous to rrhenius acti"e form of cane sugar.
n important consequence of this conceptual patching of the reducing
theory is that in the reduction the reduced theory cannot be eliminate+@ it
retains its o$n status as a "alid theory of a phenomenon.
#he ,omparison 'and to some degree competition+ of se/eral reducing
theories is the second important feature of this particular test case. =pecifical-
ly, the three formulations of the Eyring equation that are of interest are the
collision theory, the thermodynamic formulation, and the statistical mechan-
ical formulation. ll of these three theories remain "alid in the explanation.
In this $ay, ,omparison of the "arious approaches is used to illuminate "ari-
ous aspects of the mechanisms of chemical reactions.
It is harder to read this second feature as one that is inherent e"en in a
liberal reading of &agels model, e"en though it does pro"ide clues as to ho$
one might go about e"aluating the reducti"e strength of the three theories
in"ol"ed. #he e"aluation of such a reducti"e strength, combined $ith the as-
sociated theory sur"i"al, $ould form an interesting extension to &agels
model. E"en $hile it seems possible to extend it in this particular $ay, it is
interesting at this point to in"estigate $hether non-reducti"e theories pro-
"ide us $ith an a"enue to accommodate this feature more naturally.
5arden and 9aulls concept of interfield theories 'or Harris interdisci-
plinarity+ as an approach to the explication of absolute reaction rate theory
are certainly promising in this regard. bsolute reaction rate theory fits $ith
the idea of an interfield theory in the sense that it pro"ides ne$ connections
bet$een not only chemistry and statistical mechanics, but also bet$een can-
didate reducing theories from different fields such as thermodynamics. =imi-
larly, the theory necessarily dra$s on concepts from chemistry, physics, and
thermodynamics to pro"ide its o"erall explanation, since the insights offered
by the absolute theory depend in significant measure upon the comparisons
bet$een the different reducing candidate theories.
#he fulfillment of the remainder of 5arden and 9aulls criteria seems a
bit more problematic, in the sense that the theory does not refocus our atten-
tion on pre"iously neglected items or domains or predicts ne$ such items or
domains. #he theory is open to further concretization, and has to some de-
gree initiated ne$ areas of research. Ha"ing said that, the first t$o criteria
seem to be the !ey criteria that allo$ us to classify the theory as an inter-
field theory, so that 5arden and 9aulls model is at least partially successful.
Ho$e"er, $hile the case at hand fits some of the criteria for such an inter-
0he 1nity of Chemistry an+ Physi,s *2*
field theory or interdisciplinary entity, it lea"es the issue of reduction
some$hat unsatisfactorily unresol"ed.
5arden and 9aulls notion of interfield theories is usually ad"ertised as a
non-reducti"e theory, and its use seems to prompt us to come up $ith a ne$
model for the unity of science. It can be argued, ho$e"er, that their model of
interfield theories is reductionist in the sense that it ascribes to some sort of
deri"ation or explanation and at the same time liberalizes &agels reduction
postulates to include constituti"e theories. #his seems to me a defensible
classification to the extent that 5arden and 9aull seem to ha"e an issue $ith
reductionism and elimination rather than reduction as a more liberal theory
of explanation.
#he &eurathian model, li!e that of 7o!ulich, is based on structural rela-
tionships bet$een the "arious constituting theories. =uch structural relation-
ships do exist, as $e ha"e already argued, bet$een the notion of the transi-
tion state and the acti"e form of cane sugar studied by rrhenius. #hey also
exist bet$een the three competing theories@ the form of the mathematical
equations for the reaction rate constant is similar.
&one of the non-reducti"e models, moreo"er, are incompatible $ith the
"ie$ of the net$or! of intertheory relations $e ha"e s!etched in 0igure ;,
$here &agelian connections exist bet$een the different theories that form
the net$or!, and $here the o"erall reduction is specified in terms of this
net$or!. #herefore at this stage there seem to be no good reasons to con-
clude that a &agelian model cannot fruitfully deal $ith the complexities of
theory comparison in the present case.
/. 1onclusion@ the unity of chemistry and physics
&aturalized &agelian reduction has yielded interesting perspecti"es on the
case of absolute reaction rate theory. 9y aim in this conclusion $ill be to
gather up some of the gains and suggest a"enues for further $or!.
#he heuristic approach to &agelian reduction follo$ed in this paper has
suggested that the t$o salient features of absolute reaction rate theory M the
specification of the transition state and the explanation by comparison
through the "arious reducing theories M necessitate a realignment of &agels
model of reduction along the lines suggested by 4lein '()).+ and 5izad6i-
7ahmani et al. '()*)+, and more formal $or! to extend this model to the no-
tion of a theory net;or-.
#he explanation by comparison feature of absolute reaction rate theory
also suggests interesting additional formal $or! in the philosophy of science,
in $hich se"eral candidate reducing theories can be e"aluated on their explan-
*2( Hinne Hettema
atory strength. feature of such a 'future+ formal de"elopment $ill ha"e to
be that it accounts for the insights offered by the "arious candidates for the
reducing theories. It also needs to clarify $hy these candidates are not elimi-
nated.
s the current example suggests, the unity of science is most properly
concei"ed as a net$or! of interloc!ing theories, $hich pro"ide mutual sup-
port to each other. #his seems at first sight more compatible $ith the "arious
non-reducti"e theories $e ha"e discussed than $ith the &agelian model.
Ho$e"er, a large dra$bac! of the non-reducti"e schemes is that they do not
allo$ for further specification and e"aluation of the consequences of this fact.
#he reducti"e model, e"en in places $here strict &agelian reduction fails, at
this point appears to be the superior science of science.
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B!1B, 2u,-lan+, #e; 4ealan+F hhet!!1Gau,-lan+uni.a,.n9