Chemical Equifibrium and

Newton's Third Law of Motion:

Ontogeny/Phylogeny Revisited

MANSOOR NIAZ
Universidad de Oriente

ABSTRACT: Evolution of the concept of chemical equilibrium has been strongly

influenced by Newtonian mechanics. Even in the late nineteenth century scientists
viewed chemical equilibrium as resulting from an equality of the contending forces,
that is, the forward and the reverse reactions. The main purpose of this article is
to show that freshman students conceptualize the rates of the forward and reverse
reactions in chemical equilibrium as forces, perhaps in the same sense as used in
the evolution of the concept of chemical equilibrium and student misconceptions
about Newton's third law of motion. Results obtained show that at least some
students consider the forward and reverse reactions as a sort of chemical analogue
of Newton's third law of motion. Based on this interpretation, it is plausible to
hypothesize that student conceptualization of the forward and reverse reactions as
forces is ontogenetically (Piaget & Garcia, 1983) a step towards the deeper
understanding of a dynamic chemical equilibrium, leading to a progressive
'problemshift' (Lakatos, 1970).
In spite of the eommonalities between
psychogenesis and the history of science, it is important to point out that
ontogenesis is not an exact and detailed recapitulation of phylogenesis. Results
obtained in this study and their interpretation are important, as they help us to
anticipate student utilization of Newton's third law in understanding chemical
equilibrium, before the dynamic nature of equilibrium is understood.
KEYWORDS:
genetic epistemology, ontogeny, phylogeny, progressive
"problemshifts," idealization, chemical equilibrium, Newton's third law of motion.

Interchange, Vol. 26/1, 19-32, 1995.

9 Kluwer Academic Publishers. Printed in the Netherlands.

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MANSOOR NIAZ

A Framework to Understand the Building of Models by Students

and Scientists

The main purpose of this article is to show that student conceptualization

of the rates of the forward and reverse reactions in chemical equilibrium
can be considered as models, perhaps in the same sense as used in the
history of evolution of the concept of chemical equilibrium and
misconceptions about Newton's third law of motion.
Following Galileo's method of idealization, scientific laws being
epistemological constructions do not describe the behavior of actual bodies
(Kitchener, 1993; Matthews, 1987; Niaz, 1993a). The process of building
models, that is, idealization is an important characteristic of modern nonAristotelian science and has been emphasized by Piaget (1970): "The
whole history of physics is about decentration, which reduced to a
minimum the deformations introduced by an egocentric subject and based
this science to a maximum on the laws of an epistemic subject" (p. 16).
With this background it is instructive to compare Lakatos' (1970, pp. 135136) rational reconstruction of Newton's research program, as a sequence
of evolving models (degree of idealization) that finally led Newton to
incorporate interplanetary forces, perturbations, bulging planets rather than
round planets, and so on. Another example of idealization familiar to
educators is Piaget's genetic epistemology (Kitchener, 1986; Niaz, 1991).
Kitchener (1987) considers Piaget's genetic epistemology as a philosophy
of science and that, "Piaget attempts to explain the growth of knowledge
in ways similar to those of Popper and Lakatos, namely, as being a rational
reconstruction of the course of epistemic change in which epistemic
transitions occur by virtue of certain normative principles" (p. 365).
The above reconstruction from the history of science shows that if
scientists adopt the methodology of idealization (simplifying assumptions)
in order to solve complex problems, it is plausible to hypothesize that
students adopt similar strategies in order to facilitate conceptual
understanding. The relationship between the process of theory development
by scientists and an individual's acquisition of knowledge has been
recognized by philosophers of science and science educators (Duschl &
Gitomer, 1991; Kitchener, 1986, 1987; yon Glasersfeld, 1989). At this stage
it is important to point out that in spite of the commonalities between
psychogenesis and the history of science, Piaget does not endorse the
biogenetic law, that is, "ontogeny recapitulates phylogeny" (Kitchener,
1985). More recently, Garcia (1987) has clarified the Piagetian position:
"there are common mechanisms underlying both individual development

CHEMICAL EQUILIBRIUM

21

and the development of science. However, let us say very strongly that this
hypothesis has nothing to do with the classic idea of a relationship between
ontogenesis and phylogenesis" (p. 128).
Finally it can be hypothesized that as scientists build models of
increasing complexity, which lead to epistemic transitions (i.e., increase
heuristic/explanantory power of the models, el., Lakatos, 1970, p. 137),
similarly students build a series of evolving models that increase in
conceptual understanding.

Student Understanding of Chemical Equilibrium

Chemical equilibrium is considered to be one of the most difficult topics
in the general chemistry program (Stewart, Finley, & Yarroch, 1982).
Various studies (Bannerjee & Power, 1991; Camacho & Good, 1989;
Gussarsky & Gorodetsky, 1988; Hackling & GarneR, 1985; Hameed,
Hackling & GarneR, 1993; Johnstone, MacDonald, & Webb, 1977; Maskill
& Cachapuz, 1989; Wheeler & Kass, 1978) have investigated student
difficulties in the topic. In a recent study Niaz (in press-a) has investigated
student understanding of chemical equilibrium. Some of the items used in
the study and the results obtained are summarized in Table 1.

Table 1

Student Performance on Items of Chemical Equilibrium (N = 78)

No. of Students with

Correct Response (%)

Item

1. A certain amount of NO(g) and Cl:(g) are

introduced in a vessel and the temperature is
maintained constant. After the equilibrium is
reached a certain amount of NO(g) is introduced
into the vessel. 2NO(g) + C12(g)
2NOCI(g) (all<0). As a consequence it can be
concluded:
Item la:

Reverse reaction rate decreases.

12 (15)

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MANSOOR NIAZ

Table 1 (continued)

Item lb:

Item lc:

Item ld:

Forward reaction rate increases

instantaneously.

47 (6o)

Initially the reverse reaction rate

remains constant.

23 (30)

Reverse reaction rate increases gradually

24 (31)

. A certain amount of NO(g) and C12(g) are introduced

in a vessel at a certain temperature. 2NO(g) +
C12(g) ~
2NOCI(g) (all<0). After the equih'brium is reached the temperature is increased
and as a consequence it can be concluded:
Item 2a:

Forward reaction rate decreases.

(3)

Item 2b:

Reverse reaction rate increases.

49

(63)

Item 2c:

Forward reaction rate increases

gradually.

21 (27)

When the equilibrium is re-established,

the equilibrium constant remains the
same.

21 (27)

Reverse reaction rate would be greater

than the forward reaction rate.

38

When the equilibrium is re-established

the equilibrium constant decreases.

32 (41)

Item 2d:

Item 2e:

Item 2f:

. Consider the following reaction in equilibrium:

2C12(g) + 2H20(g ) .
,4HCI(g) + O2(g) (AH>0).
Describe the effect of the following on the position
of the equilibrium:

(49)

CHEMICAL EQUILIBRIUM

23

Table 1 (continued)

Item 3a:

Addition of O2(g).

56 (72)

Item 3b:

Addition of C12(g).

54 (69)

Item 3c:

Decrease in the volume of the vessel.

24 (31)

Item 3d:

Increase in the temperature of the

vessel.

30 (39)

It was found that students have the following difficulties in understanding

chemical equilibrium: a) after the reaction has started, the rate of the
forward reaction increases with time, until equilibrium is reached; b) when
a system is at equilibrium and a change is made in the conditions, the rate
of the favored reaction increases but that of the other reaction decreases;
c) when a system is at equilibrium and a change is made in the conditions,
students can predict the direction of the favored reaction, however, they
have serious difficulties in taking into consideration other constraints, that
determine the degree to which the reaction is favored; and d) lack of a
distinction between completion and reversible reactions. At this stage it is
important to point out that the presentation of this topic (chemical
equilibrium) in the textbooks itself may have influenced student
understanding.

Evolution of the Concept of Chemical Equilibrium

According to Lindauer (1962) "although chemical equilibrium is no longer
looked upon as a revelation of the forces which control chemical change,
much of its development arose out of just such an expectation" (p. 384,
emphasis added). Similarly, Gorodetsky and Gussarsky (1987) have pointed
out that the concept "equilibrium" acquired from physical or everyday
experience, "represents a system that is composed of two or more forces
reaching a situation of balance" (p. 189).
Although Berthollet is given credit for his emphasis on the influence
of the quantity of reactants (as compared to affinity) upon the course of
chemical reactions, as late as 1809 he still emphasized the role of

24

MANSOOR NIAZ

contending forces. Despite Berthollet's recognition of the importance of

the quantity of reactants in chemical equilibrium he still gave contending
forces undue emphasis. This is revealed in the following quotation where
he wrote "until equilibrium of the contending forces ends the operation, and
limits the effect" (emphasis added, reproduced in Lindauer, 1962). The
statement indicates that contending forces take precedence over the
quantity of reactants and the contending forces are the limiting factor in
chemical equilibrium. Berthollet used the term equilibrium, "to denote a
balance of chemical forces, exactly as the term is used in mechanics"
(Lindauer, 1962, p. 386). According to Lindauer, Guldberg and Waage,
who presented their law of mass action in 1864, initially viewed the state
of equilibrium as resulting from an equality of the chemical forces exerted
by the forward and reverse reactions. Commenting on the work of
Guldberg and Waage, Lindauer (1962) wrote "the influence of Newtonian
mechanics appears throughout this early work on chemical equilibrium, and
the idea that chemical combinations are the result of mutual attractive
forces acting between the reactants is implicit in the term affinity" (p. 387).

Dynamic Nature of Chemical Equilibrium

It was in 1884 that Van't Hoff (1896) finally presented the law of mass
action on the basis of reaction velocities and the dynamic nature of
chemical equilibrium was recognized as a consequence of the velocities of
the forward and reverse reactions being equal at equilibrium.
When a student is first introduced to the concept of "chemical
equilibrium" she/he already has a concept of "equilibrium" based on
macrophenomena, that is physical and everyday experience (e.g., see-saw,
bicycling, balance, etc.). According to Gorodetsky and Gussarsky (1987)
"the attribution of dynamism to chemical equilibrium cannot be abstracted
directly from macrophenomena, rather it is part of the model concerning
the structure of matter" (p. 189). The concept of "equilibrium" based on
macrophenomena, involves features of rest, staticity, and sidedness, whereas
"chemical equilibrium" involves a system that stresses the conception of
dynamism and reversibility.

Newton's Third Law of Motion and Chemical Equilibrium

In this section we report results of a study conducted to replicate the
previous study (Niaz, in press-a). The research design is the same as that
of the previous study and is based on twenty-seven freshman students (Ss)

CHEMICAL EQUILIBRIUM

25

enrolled in one section of Chemistry II for science majors at the

Universidad de Oriente (Venezuela). Results obtained were very similar
to the previous study and in general the Ss were found to have the same
difficulties (summarized above) in understanding chemical equilibrium.
The main objective of this article is to analyze the reasons given by three
of the Ss in order to justify their answers in Item 3 (Table 1). All three Ss
responded to Item 3b in the following terms:
The addition of C12(g) would lead to a greaterproduction of products
and in order to counteract the equilibrium the reaction would
proceed from right to left so that the previous equilibrium is
restored. (emphasis added)
The italicized part of the answer shows that the Ss started correctly by
reasoning that the addition of Cl2(g) would lead to a greater formation of
the products, and that is how according to LeChatelier's principle the
external effect would be neutralized. It is, however, the second part of the
answer that is problematic as it suggests that in order to counteract the
increase in the concentration of the products, the reaction would proceed
from right to left, which indicates that the Ss may be using Newton's third
law of motion in its algorithmic version, "for every action there is an equal
and opposite reaction" (Brown & Clement, 1987). On the other hand, a
correct understanding of LeChatelier'sprinciple would lead to the following
reasoning: "the system adjusts to reestablish equilibrium in such a way as
to partially counteract the imposed change" (Hackling & Garnett, 1985,
emphasis added). Thus according to LeChatelier's principle the imposed
change is the addition of C12(g) and as a consequence the system
counteracts by increasing the rate of the forward reaction. It is quite clear
that the Ss consider the increase in the rate of the forward reaction as the
imposed change and that the system counteracts by increasing the rate of
the reverse reaction. Apparently, this reasoning is in accord with
misconceptions about forces in general and the third law in particular
(Brown & Clement, 1987). It is important to note that in Item 3b of Table
1 that after an increase in the rate of the forward reaction the rate of the
reverse reaction also increases gradually, till equilibrium is established.
Viewed from this perspective it can be argued that in a sense the Ss are
saying the same, that is, "the reaction would proceed from right to left so
that the previous equilibrium is restored." Empirical evidence against this
interpretation is provided by the fact that all three Ss responded incorrectly
to Items la, lc, and ld (see Table 1), which are based on the

26

MANSOOR NIAZ

understanding that if the concentration of a reactant increases after

equilibrium is established, it leads to an increase in the rates of both the
forward and the reverse reactions (Hackling & Garnett, 1985).
The same three Ss responded to Item 3d in the following terms:
As the reaction is endothermic, on increasing the temperature much
more heat would be absorbed, which leads to the production of more
products and in order to counteract the effect, the reaction would
proceed inversely, that is, from right to left. (emphasis added)
Once again the Ss start off correctly by reasoning that on increasing the
temperature the forward reaction is favored. Later, however, the Ss
suggest that in order to counteract the increase in the concentration of the
products, the inverse reaction is favored. It appears that the Ss consider
the rates of the forward and reverse reactions as forces, perhaps in the
same sense as used in the evolution of the concept of chemical equilibrium
(Lindauer, 1962) and Ss misconceptions about the third law of motion
(Brown & Clement, 1987). Furthermore, it is quite clear that the Ss
consider the increase in the rate of the forward reaction as the imposed
change and that the system counteracts by increasing the rate of the
reverse reaction. Students do not interpret the increase in the rate of the
reverse reaction as resulting from the dynamic nature of chemical
equilibrium, and this is substantiatedby the fact that all three Ss responded
incorrectly to Items 2a and 2c (see Table 1).
It is interesting to note that two of the Ss responded to Item 3c
correctly and although none of three Ss responded to Item 3a correctly, the
reasoning employed does not reflect the misconception about Newton's
third law of motion. It appears that the Ss perhaps invoke the third law,
that is, for every action (forward reaction) there is an equal and opposite
reaction (reverse reaction), only when the forward reaction takes place
from left to right.
These results indicate that at least some Ss conceptualize chemical
equilibrium as a product of opposing forces ("Force" interpretation), rather
than a dynamic equilibrium based on the rates of the forward and reverse
reactions. In order to determine if the Ss would select the "force"
interpretation in the presence of the correct response the following item
was given to seventy-seven freshman Ss enrolled in two sections of
Chemistry II (science majors) at the Universidad de Oriente (Venezuela).

CHEMICAL EQUILIBRIUM

27

Table 2

Student Selection of the 'Force' Interpretation in the Presence

of the Correct Response (N=77)
Item

No. of Students

Responding(%)
Consider the following reaction in equilibrium:
2C12(g) + 2H20(g) .
,4HCI(g) + O2(g) (all>0).
Describe the effect of the following on the
position of equilibrium:
Item a:

Addition of C12(g).
Select one of the following responses and justify it:

al

a Z"

a3
Item b:

On adding C12(g) more products will

be produced and in order to counteract
the effect, the reaction would proceed
from right to left.

18 (23)

On adding Cl~(g) the system must

counteract, and consequently the rate of
the forward reaction would increase.

43 (56)

None of the previous.

16 (21)

Increase in the temperature of the vessel.

Select one of the following responses and justify it:

bl"

As the reaction is endothermic, an

increase in temperature would lead to the
absorption of heat and the system must
counteract, leading to an increase in the
rate of the forward reaction.

44 (57)

28

MANSOOR NIAZ

Table 2 (continued)

b2 ~

b3

As the reaction is endothermic, an increase

in temperature would lead to the absorption
of heat, producing more products and in
order to counteract the effect the reaction
would proceed from right to left.
None of the previous.

25 (32)
8 (10)

'Force' Response.
"

Correct Response.

It can be observed that responses al and b2 represent the "force"

interpretation as utilized by the Ss in the replication study discussed above.
Table 2 shows that almost one-fourth of the Ss accepted the "force"
interpretation (response al) in Item a and about one-third of the Ss
accepted the "force" interpretation (response b2) in Item b. Although a
little over half of the Ss selected the correct responses in Items a and b
(i.e., a2 and bl), only 29 (38%) Ss selected the correct response in both
Items a and b. Similarly, Ss using the "force" interpretation seem to shift
strategies, as only 9 (12%) Ss selected the "force" interpretation in both
Items a and b. Again, only 5 (7%) Ss selected the response, "None of the
previous" (items a3 and b3) in both Items a and b. It is interesting to
analyze the justification given by Ss who selected response a3. Some of
them reasoned in the following terms:
In order to increase the concentration of the products, the
concentration of the reactants must decrease. Nevertheless, this does
not imply that the rate of the forward reaction must increase.
It seems that these Ss do understand that in order to decrease the
concentration of the reactants (the effect of adding C12(g)), the
concentration of the products must increase. However, this expectation is
not associated with the correct response a2, apparently because the Ss do

CHEMICAL EQUILIBRIUM

29

not have a conception of the dynamic nature of chemical equilibrium,

based on the rates of the forward and reverse reactions. Some Ss even
added:
The rate of the forward reaction does not increase because C12(g) is
not a catalyst.
These responses lead us to conclude that those Ss who selected response
a3, have a conception closer to that of the "force" interpretation (response
al), than that of the correct response a2. Similar cases were found in Item
b.
Conclusion

This article has shown that at least some students consider the forward and
reverse reactions as a sort of chemical analogue of Newton's third law of
motion. Student difficulty is compounded further, by the fact that they
adopt a concept of force as an innate or acquired property of objects,
rather than as arising from an interaction between two objects, which leads
to an epigrammatic version of the third law, "for every action there is an
equal and opposite reaction" (Brown & Clement, 1987). If we accept this
interpretation then it is plausible to hypothesize that student
conceptualization of the forward and reverse reactions as forces is
ontogeneticaUy (Piaget & Garcia, 1983) a step towards the deeper
understanding of a dynamic chemical equilibrium. This interpretation is
reinforced by the fact that as late as 1864, chemical equilibrium was
conceived of as resulting from an equality of the chemical forces exerted
by the forward and reverse reactions and the influence of Newtonian
mechanics on the evolution of chemical equilibrium, as recognized in the
literature (Lindauer, 1962). It is important to point out that ontogenesis
is not an exact and detailed recapitulation of phylogenesis (Piaget &
Garcia, 1983). For a critical appraisal of the recapitulation law see Langer
(1988).
Results obtained can also be interpreted within a Lakatosian
framework, which has been the subject of recent research in science
education (Gilbert & Swift, 1985; Linn & Songer, 1991, Niaz, 1993b, 1993c,
1994, in press-b). It is plausible to hypothesize that as scientists build
models of increasing complexity, which lead to epistemic transitions (i.e.,
increase heuristic/explanatory power, cf. Lakatos, 1970, p. 137), similarly,
students build a series of evolving models (progressive transitions), leading

30

MANSOOR NIAZ

to greater conceptual understanding. In the present case there is a

progressive "problemshift" (Lakatos, 1970) between the model which
represents chemical equilibrium as resulting from an equality of the
chemical forces and the model that represents the dynamic nature of
chemical equilibrium.
Results obtained in this study and their interpretation are important,
as they help us to anticipate student utilization of Newton's third law in
understanding chemical equilibrium, before the dynamic nature of
equilibrium is understood.

ACKNOWLEDGMENT
This work was made possible by a grant from the Consejo de Investigation of
Universidad de Oriente (Project No. CI-5-023-00628/93-94).

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Author's address:

Universidad de Oriente
Apartado Postal 90
Cuman~i, Estado Sucre
Venezuela