edlted by J.

DUDLEY HERRON Purdue University West Lafayeite, Indiana 47907

Teaching

about "Why do C h e m i c a l R e a c t i o n s
Occur": G i b b s F r e e E n e r g y

covered in chemistry courses prior to any discussion of Gihhs Free Energy, the rearrangement of eqn. (1) can serve as a starting point.
AH= AG

+TAS

Steven N. Vamvakis Delsea Regional High School Franklinuille, N.J. 08322 Joseph S. Schmuekler Temple Uniuersity Philadelphia, Pennsyluania 19122 Perhaps the most thought of, yet least dealt with, question in bezinnine chemistw is. "Why do chemical reactions occur?" ~ t u d z n t c& ohservethat chemical reactions occur; they can s measure various thinas about chemical reactions, ex., temperature changes, weights of precipitates, and volumes of evolved gases. By observing chemical reactions and applying solubility rules, students can make predictions about which chemical reactions occur, and they can see what happens and even some of how reactions occur. While these topics are of prime concern in a first course in chemistry, time should he used in answering the elusive qnestion, why do chemical reactions occur? In answering this question, some teachers invoke "fundamental properties" as a way of dealing with the question, others put the blame on "enthalpy," while still others spice up this answer with dashes of "entropy," but rarely do they present a more complete answer. To deal with the topic of "Why do chemical reactions occur," we must deal specifically with the topic of Gibbs Free Energy.
AG=AH-TAS

This equation says that; Change in = Change in + ( ~ e m p K X Change in) O entropy enthalpy free energy Change in useful Change in energy energy of the of reorganization system of the system system The answer to qnestion 2 above is essentially the same as that for the original question of this article. Numerical values of AG for specific reactions are indicators of why chemical reactions occur. Generally, the values of AG and their corresponding meanings can be summarized as follows. Change in total energy of the
=

Table 1. A Constant Temperature and Pressure t

Statement

Reason

1. G = H - TS 2. AG = Gp - G, 3. AG = (H. - T.S.) (H, - T,s,I 4. AG = H. - T.S. . - H, T,S, . . 5. AG = H, H,- TpSo T,S, 6 . AG = ,H, - H, - TS, TS,

1. Given 2. Definition of AG 3. Substitution law

4. Distributive law

+ + +

7. A G = A H -

TSp

+ TS,

5. Commutative law 6. To = T, because T is a constant. therefore Tmay be substituted for T, and T, 7. H, H, = AH, fmm definition of

(1)

AH
8. AG= A H 9. A G = A H -

Where AG is the change in Gihbs Free Energy, AH is the enthalpy change and A S is the change in entropy. An~roachine t o ~ i of Gibbs Free Eneravfrom the stuthe c it is possible den?; prior experience in algebra and to construct a proof that should enable the students to explain the derivation of eqn. (1) (see Table 1).As further explanations of the proof are needed, they can be found in Tahle 2. Though tl& proof.does nor totally cover the topic of Gihbs Frw Enrrry, 11 ( a n he used toshow the logicofeqn. ( 1 I without the useof calculus. The proof may also serve a starting point for the students to build a mental model or construct of Gibbs Free Energy. Some possible ways to consider the topic are suggested by the following questions
11 Cnn y w ~ivenn overview of the topic, (;ilhs Free Energy? 2) Of what use ir knowmg the value o f AC fur a given reaction? 31 Can begmniny rhern~rtrystudents underitand a calrulotion of
AC?

T(Sp- S,) TAS

8. Distributive law 9 . S, - S, = A S from definition of

E=G,MS,and T
B. = B of the oroducts J = J a f the reactants , G = Gibbs Free Energy

AS H = Enthalov ,, S = Entropy T = Temperature ( O K )

Table 2. Expanded Explanations for Corresponding Reasons in Table 1

1 Step (11 is given! All poofs start with a given statement W t the proof builds . from. It might also be stated that statement ( I ) is the definition of Gibbs Free
Energy. 2. Step ( 2 ) may need more explanation if the symbol A is new to the st". dents. 3. Stsp (3) can be arrived at by a combination of steps (I) (2). and 4. A short review of how to properly remove parenthesis might be in ardet here. 5. Straight forward. 6. T!w reason ta step (6)m i m be repeatedmroughouth proof. It is impatanl for W student to realize that me conditions in which mey or most chemists normally work are usually at constant temperature and pressure. 7. Same as item ( 2 )above. 6. YOUare using the distributive law in reverse to its applicatibn to step (4). 9. Same as item (2) above.

In answering qnestion 1,an approach from basics is again in order. Since changes in enthalpy, or heat of reaction, are B<,thnuthmsu,ere involvrd in the ACSl'nsk Forrson High School to fur Chcn,iitryl'r~rhrrt ile\.rl<,l,'.(;t~idel~nes the Preparation and Ctwnmislry 'I'eachem." ('ontinuma Edurnrwn of ircmdory Sch~ol

Volume 54, Number 12, December 1977 1 75:

fAG

>0

The reaction is not spontaneous. Energywill have to be added to the system in order for the reaction to
occur.

Based on this information1 above, one might predict t h a t the reaction will not occur. S%(g) = 0.0591 kcalPK mole So&) = 0.0279 kealPK mole
S'aJg) = 0.0533 kcalloK mole

[f A G = 0 If A G

<0

The system is at equilibrium. The forward and reverse reactions are negating any increase in concentration for products or reactants. The reaction is spontaneous. Energy will not have to be added to the system in order for the reaction to occur.

Using eqn. (1)stated earlier,

AG = A H - T A S AG = (2) X 4.20 kcallmole - 298OK [(2) X 0.0591 kcalPK mole - (0.9279 kcalPK mole 0.0533 kcalPK mole)]

The "purist" will note that we have not mentioned the work ione bv the svstem a s is usuallv done in discussine the meaning ~t'valuesior AC. The ability ro"sev" the w n w p t of uork beinr owformed in a beaker llask is nor evident LO all -. ;eachers of beginning chemistry. The omission is meant t o woid confusion by the novice. T o answer question 3 above, you need only perform a cal:ulation. T h e most dramatic calculations are for endothermic .eactions t h a t d o proceed spontaneously. A common example s the reaction between solid I2 and gaseous Clz a t 25'C and 760 torrs. Ids) + Cl,(g) 2ICl(g) AH,,ti,, = + 4.20 kcallmole

note: (2) in the above equation refers to the stoichiometry of the reaction.
AG = 8.40 - 11.03
= -2.63 kcall2 moles ICl(g)
= -1.32

kcal/mole IClCg)

Therefore a spontaneous reaction will occur! General References Campbell,J.Arthur, "Why Do Chemical Readions Occur?"PrenticeHall, Ine.,E n g l e d Cliffa, N.J., 1965. Choppin. G., 6.Jsffc, L. Summerlin, L. Jsckson;'Chemistry," Silver B"rdettCo,Ma.riatown.N.J.. 1973. Metralfe, etal.."Modern Chami8Uy:'Holt. Rinehart and Winston, Ine, Nea York, 1970. Mmre. "Physical Chemistry,"4th M., Prentic~ Hell. Englewiwd Cliffs, N.J.. 1972. Circular of the National Bureau of Standards. 5W, Washington. D.C.. 1952.

Data for this calculation taken from Circular 5W of the National Bureau of Standards, Washington, D.C., 1952.

758 / Journal of Chemical Education