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Physical Chemistry 2012, 2(4): 43-47

DOI: 10.5923/j.pc.20120204.01

C = C r, A Silver Bullet for Evaluation of Components


in Simple Equilibrium Reactions: The Relation Revisited
R. Sanjeev 1,*, V. Jagannadham2 , R. Veda Vrath3

1
Department of Chemistry, M izan-Teppi University, Teppi Campus, Teppi, Ethiopia
2
Department of Chemistry, Osmania University, Hyderabad, 500007, India
3
Department of Chemistry, L N Gupta Evening College, Hyderabad, 500002, India

Abstract Phase rule is an integral part of the undergraduate curriculu m in many universities across the globe. In an
appreciable nu mber of un iversities, it is dealt with in the fresh man year. The students find it ext remely confusing to find the
number of co mponents even in simple equilibriu m react ions. Normally they end up giving wrong answers, or if at all they
give correct answers, they are just conjectures. To overcome this overwhelming confusion we have first considered different
simp le and relatively unco mplicated equilibriu ms fro m standard physical chemistry books and research journals. In these
different equilibriu ms first we evaluated the number of components as illustrated in the books. In each of the book, dissimilar
methods were emp loyed to evaluate the number of co mponents which is not a straightforward task for the freshmen students.
Then we presented an easy generic method which involved the use of the less involving relation C = C r. Our endeavour in
this article is to present a terse and lucid method, by means of wh ich the nu mber of co mponents can be evaluated. Finally, one
feels, after going through this article, that this convenient and handy relation C = C r is undeniably a silver bullet for the
evaluation of components in simp le and relat ively less complicated equilibriu ms.
Keywords Phase, Co mponents, Restrictions, Constituents, Phase Rule

handy relation enables easy evaluation of components in


1. Introduction various equilibriu ms, especially for freshmen students.
Even in the case where large amount of imagination is
It has been found that one of the most difficult areas in required to evaluate the co mponents, the relat ion C = C r
physical chemistry at freshmen level is the phase rule, comes to aid.
which requires large amount of imagination on the part of
the students when it co mes to evaluation of the nu mber of
components, one of the vital terms in phase rule. Even
3. Method
though there are easy formu lae to overco me this Since th is article involves the use of the handy relation C
requirement, the students are not made aware of. One such = C - r, the method is less involving. The evaluation of
formula is C = C r for the evaluation of nu mber of components of various equilibriu ms fro m standard physical
components C. Here C is the total number of nu mber of chemistry text books and research journals are examined.
chemical constituents in the system, and r is the number of Finally the easy evaluation of the co mponents using the
restrictions imposed on the independent variation of these handy relation is presented and verified.
constituents. In this article, we have shown how the use of
the relat ion C = C r is far more superior to the other
methods when it comes to the ease of evaluation of number 4. Discussion
of components.
Most of the textbooks give the example of decomposition
of calciu m carbonate reaction to illustrate the evaluation of
2. Objective number of co mponents in an equilibriu m reaction (and so
does Glasstone1 ).
As described in the title the very purpose of writing this CaCO3 (s) CaO(s) + CO2 (g)ref. 1 (1)
article is to revisit the relation C = C r. Th is generic and It might appear, at the first sight, that there are three
components, viz., CaCO3 , CaO and CO2 , but it is evident
* Corresponding author:
that these substances are not independent, as required by the
rachuru1sanjeev1@redi ffmail.com (R. Sanjeev)
Published online at http://journal.sapub.org/pc definit ion of the co mponent; thus CaCO3 is really
Copyright 2012 Scientific & Academic Publishing. All Rights Reserved equivalent to CaO + CO2 . The two co mponents may
44 R. Sanjeev et al.: C = C r, A Silver Bullet for Evaluation of Components in Simple
Equilibrium Reactions: The Relation Revisited

consequently be taken as CaO and CO2 , so that the decomposition of calciu m carbonate (as already exp lained).
composition of calciu m carbonate can be represented as The solvolysis of benzyl-gem-dich loride4,5 is depicted in
xCaO + xCO2 , that of the calciu m o xide as y CaO + 0CO2 , scheme 1 (for X Cl).
while that of carbon dio xide gas phase is 0CaO + zCO2 . The
H O H
two components might equally have been chosen as CaCO3 X X X + H
C
and CaO, when the composition of the gas phase would be
given by zCaCO3 - zCaO. The actual nature of the ksolv ks
components is not important; it is their nu mber that is -
kX[X ] +H2O, - HX
significant, and this should always be the same for a given Y Y Y
system if the components are chosen properly. Scheme 1. Depicting the solvolysis of benzyl-gem-dichloride
We shall now consider other examples. Let us take the
example when ethanol2 and acetic acid are mixed. At the In our earlier study 5,6,7,8 wherein we had sought insight
first sight, we might predict two co mponents because there into the mechanism of this react ion by testing the
are two constituents viz. HOAc and Et OH. However these conformity of the data to the Hammetts equation, the first
constituents react to give ethyl acetate and water. Therefore equilibriu m step and the subsequent step, were considered
ethyl acetate and water are also present at equilibriu m separately. It would be instructive to treat the equilibriu m
together with the reactants. This raises the number of separately. In this simple solvolysis reaction, the solvolysis
components fro m 2 to 4. step involves a simple equilib riu m. The equilibriu m
HOAc + Et OH EtOAc + HOH (2) constant can be written as Keq = [-chloro-carbocaton]/[ben
But because of equilibriu m condit ion and since at zyl-gem-d ichloride]. Fro m the knowledge of Keq and the
equilibriu m [Et OAc] = [HOH], the number of co mponents concentration of any one of the species -chloro-carbocatio
is reduced back to 2. n or benzyl-gem-d ichloride the concentration of other can
If we consider the examp le of deco mposition of pure be obtained. Thus the number of co mponents is one. In a
PCl5 ref.2 , similar manner, in the equilibriu m of solvolysis of
PCl5 (g) PCl3 (g) + Cl2 (g) (3) benzyl-gem-dibro mide6 and benzyl-gem-diazide7 , the
Three chemical species are apparent but the number of number of components obtained would be one.
components is reduced to one. This is because of equilibriu In the above simp le ten equilibriu ms, the manner in
m condition and the relation [PCl3 ] = [Cl2 ]. which the co mponents are evaluated is not the same for all
The solution of acetic acid 3 in water is also a case in the systems. This places a heavy toll on the grey cells of the
point freshman teenagers.
CH3 COOH + H2 O CH3 COO- + H3 O+ (4)
There are many chemical species; clearly, however, the
presence of two species can imp ly the presence of other
5. Conclusions and Results
species determined by the equilibriu m relations that exist. The system is discussed and concluded as correct when
Avoiding the strict attention to the possible equilibriu ms the result obtained from C = C r is the same as we
among the species of the system, the consideration of the imagined.
example, (gaseous system of water vapor, hydrogen and In the forgoing examp les for the illustration of evaluation
oxygen) will yield meaningful inference. In the presence of of components, uniformity in the exp lanation is not
electric arc or suitable catalyst, the equilibriu m can be maintained. Therefore a general exp ression for evaluation
described as of co mponents would be o f much benefit, both to the
2H2 O 2H2 + O2 ref.3 (5) teacher and taught. The number of co mponents in a system
This system has two components. It can be seen that if can be determined in the following general manner1 .
the concentration of any two species is arbitrarily set, the Let C be the number of chemical constituents in the
concentration of third is fixed and can be calculated fro m system, and let r be the number of restrictions imposed on
equilibriu m constant. the independent variation of these constituents. The
In the thermal decomposition of ammon iu m chlo ride, number of components C is given by the equation:
there are three chemical species. NH3 and HCl are fo rmed C = C r (8)
in fixed stoichio metric proportions by the reaction. For instance, let us apply the relation 8 to reaction 1.
NH4 Cl(s) NH3 (g) + HCl(g) (6) Here C = 3 and r = 1 i.e. the equilibriu m condition restricts
And therefore, the composition of both phases can be the independent variation of the constituents. Hence C = 2.
expressed in terms of a single species NH4 Cl suggesting In reaction 2, C = 4 and r = 2 i.e. equilibriu m and the
that there is only one component in the system. relation [EtOAc] = [HOH] restrict the independent variation
The decomposition of magnesium carbonate can be of the constituents. Hence C i.e. number of co mponents is 2.
described by equation 7. In reaction 3, C = 3 and r =2 i.e. the equilibriu m
MgCO3 (s) MgO(s) + CO2 (g) (7) condition and the relation [PCl3 ] = [Cl2 ] restrict the
There are three constituents but the number o fcomponent independent variation of the constituents. Therefore C = 1.
s is two. The exp lanation for this is same as that for In reaction 4, C = 4 and r =2 i.e. the equilibriu m
Physical Chemistry 2012, 2(4): 43-47 45

condition and the relation [CH3 COO-] = [H3 O+] restrict the The derivation of phase rule10 was first put forth by J.
independent variation of the constituents. Hence C = 2. Willard Gibbs in 1878. Unfortunately it was published in a
In reaction 5, C = 3 and r =1 i.e. the equilibriu m rather obscure journal Transactions of the Connecticut
condition restricts the independent variation of the Academy of Arts and Sciences11 and was overlooked for 20
constituents. Hence C = 2. years. The derivation of phase rule like any other
In reaction 6, C = 3 and r = 2 i.e. the equilibriu m derivations has essential concepts and assumptions
condition and the relation [NH3 ] = [HCl] restrict the embedded in it. It is here the teaching acumen o f the
independent variation of the constituents. Hence C = 1. instructor is wanting, and it is for the teacher to discern and
In reaction 7, C = 3 and r =1 i.e. the equilibriu m accentuate the number of intensive variables fixed by free
condition restricts the independent variation of the constitue energy equilibriu m relations. Let us recapitulate the phase
nts. Hence C = 2. rule obtained by J. Willard Gibbs.
In the equilibriu m of solvolysis of benzyl-gem-dich loride, Consider the C co mponents to be distributed throughout
C is 2 but the equilibriu m restricts their independent each of the P phases of a system as schematically indicated
variation i.e. r = 1. Hence C = 2 1 =1. Analogously in the in Figure 1.
solvolysis of benzyl-gem-d ibro mide and benzyl-gem-diazid To get the total number degrees of freedo m one has to
e the components can be obtained as 1 by applying our first add the total number of intensive variables required to
simp le relation C = C r. describe separately each phase and then subtracting the
Let us see a system that is a little more co mplex where in number o f intensive variables, whose values are fixed by
AlCl3 is dissolved in water9 , noting that hydrolysis and free-energy equilibriu m relat ions between different phases.
precipitation of Al(OH)3 occur, g iving various ions. Al3+, To begin, each co mponent is assumed to be present in every
H+, AlCl3 , Al(OH)3 , OH- , Cl-, H2 O are the seven species phase.
present in this system. There are also three equilibriu ms:
AlCl3 + 3H2 O Al(OH)3 + 3HCl
AlCl3 Al3+ + 3Cl-
H2 O H+ + OH-
And one condition of electrical neutrality
[H+] + [Al3+] = [OH-] + 3[Cl- ]
Hence for this system, C = 7 and r = 4 i.e. the three
equilibriu ms and the condition of electrical neutrality
restrict the independent variation of the constituents. Hence
C = 7 (3+1) = 3.
Let us take a similar but a little more co mp lex examp le9
Figure 1. Depicting C components distributed throughout each of the
where in one finds the number the co mponents of (a) P phases
Na2 HPO4 in water at equilibriu m with water vapour but
disregarding the fact the salt is ionized. (b ) The same but In each phase (C -1) quantities will be required to define
taking into account the ionization of the salt (disregarding the composition of the phase quantitatively. Thus, if mo le
the water vapour). In the former case (a) total numbers of fractions are used to measure the concentrations, one needs
constituents (C) are three, namely, salt, water and water to specify the mole fraction of all but one of the
vapour, there is an equilibriu m condition (restrict ion) components, the remain ing one being determined because
between liquid water and its vapour. Hence the total number the sum of the mo le fract ions must be unity. Since there are
of co mponents are C = 3 1 = 2; In the latter case (b) there P phases, there will be total of P (C 1) such composition
are seven (C) species: Na+, H+, H2 PO4 -, HPO4 2-, PO4 3-, H2 O variables. In addit ion, the pressure and the temperature must
and OH-. There also exist three equilibriu ms (disregarding be specified, giving a total o f P (C -1) + 2 intensive
the water vapour), namely variables if the system is considered phase by phase.
H2 PO4 - H+ + HPO4 2- The number of these variables, which are fixed by the
H2 PO4 2- H+ + PO4 3- equilibriu m conditions of the system, must now be
H+ + OH- H2 O determined. Co mponent 1, fo r example, is distributed
Further there are also two conditions of neutrality, between phases P1 and P2 . When equilibriu m is established
namely for any one co mponent distributed between any two phases,
[Na+] = [phosphates] and [H+] = [OH- ] + [phosphates] a distribution relation 12 can be written. Thus, if the
where [phosphates] = [H2 PO4 -] + 2[HPO4 2-] + 3[PO4 3-] concentration of a co mponent in phase P1 is specified, its
Hence the total numbers of restrictions are the three concentration in phase P2 is automatically fixed. Similar
equilibriu ms, and the two conditions of neutrality i.e., they equilibriu ms are set up for each co mponent between the
restrict the independent variation. Thus the total number of various pairs of phases. For each co mponent there are (P -1)
components (C) are C = 7 (3 + 2) = 2. such relat ions. Thus, for C co mponents a total of C (P -1)
The comp rehension of the important term restriction is intensive variables are fixed by equilib riu m conditions.
better understood if one studies the derivations of phase rule. The number of degrees of freedom, i.e., net adjustable
46 R. Sanjeev et al.: C = C r, A Silver Bullet for Evaluation of Components in Simple
Equilibrium Reactions: The Relation Revisited

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Physical Chemistry 2012, 2(4): 43-47 47

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