THE LAW OF PHYSICO-CHEMICAL CHANGE.

By Gilbert Newton Lewis.

Received April 6, 1901. Presented by T. W. Richards, April 10, 1901. Introduction.

The
in recent

many-sided
years has

application of thermodynamics
led to a maze of mathematical

to physical chemistry
expressions which is

bewildering
great upon or majority the two

to the beginner
of laws these of

and confusing
but not not

even to the initiated.

formulae are some true, too based not upon

The
only law in

physico-chemical

approximation, so far as the system

thermodynamics and are as a rule considered does

also

rigorously deviate

empirical but are useful from

widely reason

certain

ideal conditions.
which tinued are not

The
strictly existence

difficulty
exact of

of

treating mathematically
chief of for which, formulae

equations
the con

though are in form. It seemed not identical, similar that tantalizingly probable if the present in any way formulae could be replaced exact by rigorously or concreteness without immediate then ones, sacrificing applicability, so serve exact be that one these systematized equations might might a number are now in use, with a of isolated where equations great gain in view in simplification. the present With this object has investigation success a the unexpected carried of been law on, and with finding single which and The upon the 1. 2. yet is simple, concrete to in itself many laws general comprise enough to be to cases. immediately enough applicable specific will be based four laws of nature and upon development or of any kind. These are laws hypothesis assumption exact, law of law

separate

the is probably the large number

following no other following first The The ?:

second

thermodynamics. of thermodynamics.

3. Every gas, when rarefied indefinitely, approaches a limiting condi tion in which Pv = ET, (1)
if P the represents absolute pressure ; v, molecular volume ; R, the gas constant ; T,

temperature. VOL. XXXVII. ? 4

50 4. Every in which
if II represents The present

PROCEEDINGS OF THE AMERICAN ACADEMY. solution diluted indefinitely approaches n v = R T, (2)

osmotic paper pressure. will discuss the laws which govern systems com

a limiting condition

posed of a single, chemically

second paper in which the

simple, substance, and will be followed by a

governing I. mixtures will be studied.

laws

Clausius*

Formula

Simplified.

Clausius
change, equation the

showed that if Q represents

second law of thermodynamics

the heat change

may be

in a reversible
by the

expressed

T
which is valid for every cyclic process

dT

W
that since in a cycle

; moreover,

there is no change
cycle, finite and change that when of volume

in internal energy, d Q represents

the process is one in which and the no at constant pressure, other

the work

of the
a

system

undergoes is done, work

?e
where volumes. liquid and P represents the In its vapor the specific we

rfP(Fi-Fa),
and in which the Vx and the V2 the and original is composed final of a

pressure case obtain

system

equation

Q _ Qi

tt2) dp

T~
in which of one p represents vapor ; and pressure vx and

dT
; Q,

'
the total heat volumes of vaporization of vapor and

gram-molecule of

v2, the molecular

liquid respectively.
the change vapor

Transposing
pressure with

the equation gives an expression

change of temperature,

for

dT

fa

W v2)T
and exact, but in practice it is derived from it if two
compared with vx, and

This equation of Clausius is both general is replaced by a simpler equation, which

assumptions therefore are made approximately, vx : First, that ?

v2 is negligible =

v2

vx.

LEWIS.

THE

LAW

OF

PHYSICO-CHEMICAL

CHANGE.

51

Second,

that

the

vapor

obeys

the gas vx = RT

law,

These

two equations substituted

~TT"~

in (4) give the familiar equation,

dlnp _
While strictly vapor neither true, they of the in perfect for as a (4), two that assumptions the

Q
RT2' made above a the cannot is true first be in any as

(5)
case the represents but liquid limit

differ the absurd,

second

approaches zero even

mathematically approach return must

in its behavior, gas the volume of a For an exact

is always made to we form.

limit.

equation,

therefore,

to equation

notwithstanding

its rather

complicated

There
appear

is in fact a lack of simplicity

in certain analogous expressions

in this equation which

that will be developed

does not
in this

paper.
exact

That
equation

this lack of simplicity

for the influence of

is, however, not inherent

on vapor pressure,

in every
but is

temperature

due rather to the complex

will It any be evident from the that changed is well substance known is

conditions

for which

equation (4) is proved,

the vapor on pressure its surface, of

considerations. following at constant temperature a in the total by change

pressure

according to the equation first obtained by Poynting,*

dP
in which lecular

*? = * V; i>!
; P, total pressure respectively. resulting on the pressure. change change the due in change

(6)
; v2 and vu mo the When, increase surface, The therefore, in vapor and this pressure in itself change is in

vapor pressure p represents and vapor volumes of liquid of a liquid is raised, the temperature an of increase further is the us in the total pressure in vapor of to the the

brings a cause vapor change surface. change constant

pressure and Let of by

change sum the due

observed

change therefore

determine the Figure

to merely temperature total the pressure upon in vapor with pressure on the surface an is kept

temperature artificial

when means.

total

pressure 1 represents

such

arrangement.

The
B D

space E D contains
contains an inert

liquid kept at constant pressure by a piston, F.

insoluble gas. B C is a membrane impermeable

to this gas, but permeable

to the vapor of the liquid used.

A B contains

* Phil. Mag., (5)XII. 32 (1881).

52
this vapor

PROCEEDINGSOF THE AMERICAN ACADEMY.

alone. A change of temperature will change the vapor pres

sure in A B without
is always equal to the

changing
outside

the total pressure

pressure on F. We

on the liquid, which

may simplify this

arrangement
regarded

by making
with

the layer of inert gas so thin that it may be

the membrane B C merely as a single membrane,

together

which

is impermeable

to the liquid but permeable

to the vapor.

In

Figure

1.

Figure

2.

Figure 2 it is represented by the dotted line B. The spaces B C and A B are filled with liquid and vapor respectively, and the pistons A and C can
be moved up and down so as to distribute the substance between the

liquid and gaseous

influence stance, cycle, while of all

phases as desired.
Let us start with and

The whole
one

is removed from the

gravity. in the liquid the which during the pressure

of the sub gram-molecule the reversible state, pass following through remains the P, C, constant, upon pressure, piston, to the vapor is always pressure. upon A equal kept

At first the piston A is at B ; the space B C has the volume v2.

temperature at the same none of the is raised time liquid from Tto the T original The -+- dT, vapor piston the pressure on A to p + down being from p, pressure, C moves

(1) The
raised that of

evaporates.

so dp, on account

the expansion, dv2, of the liquid. (2) All the liquid is evaporated at to T d + T, C moving B, and A moving up to furnish the temperature is The volume, vt. (3) temperature again brought to T; the pressure on A to p. A moves down on account of the contraction d vx. (4) All the vapor is condensed and the original condition is restored. The
amounts of work Fi = done Pdv2, by the system in the several steps are ?:

W2 = -P(v2
W* W? = = ?pdvH Pv2 ?pv^

+ dv2) +

(p + dp) Ox + dvj,

LEWIS.

THE

LAW

OF

PHYSICO-CHEMICAL

CHANGE.

53

The the

total total

amount amount

of work of heat

gained, transformed

the

sum

of

these that

terms, is,

is equal

to

into work,

Wx+ W2+ r3+

from equation (3). Adding

Wi = dQ =

?dT,

the terms we obtain,

or

writing

so as

to express

the

constancy

of P,

(dJL\ __#_ ^Tj-v.T

(7)

This important result may be derived directly from equations (4) and as liquids. Since the vapor pressure is a func (6) and for solids as well
tion write of the temperature, T, and the pressure on the surface, P, we may

?-fa),"
Now, general, in the change in vapor change in when pressure pressure, only on a pure the is, surface that

*&),"
substance of the and its vapor is are present, the substance merely

dP=dp. Moreover, ? ?^ J = ?, from equation (6), therefore,

'",-(??),",+

s'??

Substituting

for -~

from equation (4),

Q
7>i-OV

/\

v2\
VJ

[9p\
\dTJp

f9p\
\5TJp

Q
?i?

which is equation (7). We have in this equation a marked simplifica tion of the Clausius formula with no loss of exactness. We could now, by making the single assumption that the vapor obeys the gas law, throw equation (7) into the form analogous to (5), namely,

M1-?)-(&*).-(?*),

54
Instead of

PROCEEDINGS OF THE AMERICAN ACADEMY.

using this equation we may introduce here a quantity with the

aid of which it is possible to substitute for approximate equations of the type of (7) other entirely exact equations of the same form. This
quantity is one whose utility I have shown in a recent paper.* It

may

be well

to repeat and amplify

II.

the definition

there given.

FUGACITY. If with pass be any any from phase other the containing not phase molecular given that containing to the second. to have a tendency a species species, is in contact brought a certain will quantity species the phase may in

phase first

considered,

therefore,

molecular Every to escape from

which
particular example, sure, one fact

it is.
state, as

In order to express
an infinite number the thermodynamic etc. in water, at first general, sight

this tendency quantitatively

of quantities of the could be used, its vapor shall these, It will

for any
such, for pres is is called in

its solubility seems which simpler, ?: more

species, potential we The which quantity more than any of abstruse easier to manipulate.

choose but be

and

the fugacity,f
conditions 1. The

represented

by the symbol \pand defined by the following

in two phases is the same when of a molecular species fugacity as are in equilibrium the distribution of that regards species. phases as a the gas of a gas 2. The pressure approaches limiting fugacity In other the rarefied. is indefinitely if the gas value words, escaping to its gas pressure. is equal of a perfect gas tendency a to define are of every two conditions sufficient That these property these substance which is not a mathematical, experimental is obvious from methods of a of fictitious quantity, in determination above conditions are gas unable law then In the gas. all but every that to the a real case, in any show vapor the a

capable quantity, physical now be shown. It must case where of our the present vapor nearest is an the

the

of measurement from to to is the the to the

deviation pressure vapor being

substance

is the pressure nearer

approximation

fugacity. fugacity, a perfect

cases

approximation nearer the vapor

approximation When the

343 (1900). 145 (1900) ;Zeit. Phys. Chem., XXXV. Acad., XXXVI. was called the escaping and repre t In the earlier paper this quantity tendency I have chosen to substitute For the sake of brevity sented by the same symbol. " in the the slightest without for "escaping the word "fugacity change tendency" function. of the meaning

* Proc. Amer.

LEWIS.

THE

LAW

OF

PHYSICO-CHEMICAL

CHANGE.

55

behavior of the vapor deviates perceptibly

the exact value the four of the laws is a From following, coefficient perature fugacity stated may in the be found

from that of the perfect gas

as follows ? : it is easy to derive the : The tem

introduction

which of

rigorous between distribution a constant

statement a gas with

of Henry's law, namely and its solution at constant dilution. This

approaches

increasing

constant

will be designated by p. At

infinite dilution, P -n

where

is

the

gas

pressure

and

II

the

osmotic

pressure

in

solution.

Now p, at infinite dilution,

the gaseous phase, and also

is equal to the fugacity of the substance

in the solution, since the two phases are

in
in

equilibrium.

Therefore, t

pll.

(8)

That is, the fugacity of the solute in an ideal solution is equal to its osmotic pressure multiplied by p. If now it is desired to find the
of fugacity be brought any molecular in contact with species X a chosen in any solvent given and phase, the that osmotic phase may pressure

E4 of the saturated solution determined. Then by diluting this solution in contact with vapor of X the limit px of the distribution ratio may be
found and so the product px IIi. So for another solvent we may find the

product p2n2
as far as the

; for a third, p3 II3, etc.

saturated solutions deviate

These will all be equal except in

from the ideal solution. Prac

tically, the product will be the same for all solvents in which X is only the exact slightly soluble and will be the fugacity of X. Theoretically,
value vents We all cases of are see, of of the fugacity is the chosen that limit successively therefore, approached by the in which X is less and is a real A for the physical complete understanding attention will be p II, product, less soluble. quantity appreciation of further as sol

meaning

experimental this quantity In order, a further this of paper, if/ will

fugacity determination. is essential

capable of the

in the

follow our last the have

ing pages. main object, of section determination already been

however, discussion in which be

not of

to distract fugacity another

from to the for as

postponed method quantities

offered,

determined

in many

using cases.

independent such only

The great utility of this new quantity will be shown to lie in the fact
that the approximate developed obeys rigorously the gas law, may equations for except be the and vapor pressure containing the assumption that the vapor pressure of the same form by exact equations replaced

56 or of equal
pressure. Let

PROCEEDINGS OF THE AMERICAN ACADEMY. simplicity

us proceed

containing
to the

the fugacity
determination

instead' of
of the laws

the vapor
according

to which
the

fugacity
of a

changes with
substance

changes

in the variables
in the

upon which
present paper

condition

depends,

considering

only

those systems which

are composed of a single chemically

simple

substance.

III.
Influence Let and us of consider but be and Temperature two not phases necessarily in which slight an of and a Pressure substance at on the with soluble saturated the same each without Fugacity. temperature other. molecu may A

pressure, may

solvent lar

chosen to so

change,

in equilibrium are both phases extent the that

solutions

In such a case the solubility of each be regarded as infinitely dilute. phase is governed by the following equation, which may be obtained directly from equations (2) and (3),

\9T

(91nTL\

Q
RT*

)t

in which II is the osmotic pressure of the saturated solution and Q the reversible heat of solution (that is, inclusive of the osmotic work). We
may write for the two phases,

_ /SlnllA

V ST

= )

Q2

?f"2'

?r combimn&

(9)
Qx __ Q2 may be conveniently replaced in the following way. Let one

gram-molecule
then diluted or gram-molecule

of the first phase be dissolved

concentrated removed as the to the second osmotic phase.

in the solvent, this solution

pressure If these II2, and three then steps the be

done reversibly

the heat absorbed in each will be respectively Qh RT\n^, -<?2.

The

total heat change is a function only of the conditions of the two one passes into the other, and may be phases, not of the path by which designated by ?i>2, thus,

LEWIS.?THE

LAW

OP

PHYSICO-CHEMICAL

CHANGE.

57

Qlt=Ql We may

BTbi^-Qt,oT

Q1-Qi

Q1A-BTbi

Hi.

therefore write equation (9) as

51ns? 9T JP
Since we are dealing with
= i/?! p IIj and ^ , and =

<?1,2

lDn,

RT*

infinitely dilute solutions in the same solvent,

P n2, therefore

the above

equation

becomes

Slnf1
.9 T This is the desired Its form tendency.
the quantity

_Qh*__Zi*. RT2

_<A?

'

(10)

equation connecting temperature and escaping can be simplified by a slight rearrangement.

^ln ? ^2 we notice that

Considering

9 Tin

37
Combining

In fa =

Slnf1 ^2 r T. + S27

, 9Tln^
ln^,or
?As

5Z7

'

fc In ^2 '
T

9T

this equation with (10) gives

9Tln^
_]h
in this fugacity on the this form at for

. 9T
the present pressure, constant previous it the let

AT7' equation connecting us determine the I have of to

(H)
tempera of influence already using base dis the all

Leaving ture and pressure cussed general

constant at in a

fugacity

temperature. paper,# has seemed but

question there

instead preferable

equation

derived

the reasoning
introduction. Let us

of this paper directly

any simple

upon

the four laws stated in the

and a solvent, so f

consider

substance

arranged

that the pressure upon the substance

* Loe. cit. such arrangements

in question may be altered without

t Several

are described

in the paper

just mentioned.

58
changing stance pressure the from of

PROCEEDINGS OF THE AMERICAN ACADEMY.

pressure on the solvent or and out depends of without the upon preventing solvent. The the pressure the sub

freely passing the saturated

into solution

osmotic on the

If the latter is represented by P and the former by II, then substance. for P + d P the osmotic pressure will be II + d II. We may moreover
the molecular represent v? d v at pressure P by vf at osmotic pressure by volume + II, d P; by of the substance the molecular ? d v1 at II + vf by volume d II. v at in If a pressure the P, solution

gram-mole

cule of the substance at pressure P is (1) dissolved against the osmotic pressure II, (2) its solution concentrated to II + d II, (3) removed from solution against the pressure P -f d P and (4) allowed to expand from P -f- d P to P, an isothermal cycle is formed, and if each step is made reversible the total work of the cycle is zero. The work obtained in the
several steps W^Ilv1 = may be Pv, -ILdvf, W2 represented by Wly W2, etc.

W3 =
W? Writing =

(P+dP)
Pdv. sum equal

(vto zero,

dv)

(n + dU)

(V

dv')r

the

vdP?v!dIl or expressing in the equation the constancy

0, of T,

This

is an

exact solution

saturated

general and

equation the pressure Since as

connecting upon we may we desired the

the pure

osmotic solute. a solvent

pressure It

of

to equation analogous is as slightly solute

(6). soluble

choose will

is entirely in which the in which the

choose

one

solution may be regarded as infinitely dilute. RT v' from equation (2). Combining

Then,

this equation with

(12) we obtain

From equation (8),

= \j/

p II. /?)lni/A

Therefore __ /31nn\

= In \j/

In II +

In p, and

\9P

Jt"\

9P )t

LEWIS. ?

THE

LAW

OF

PHYSICO-CHEMICAL

CHANGE.

59

since becomes

is

constant

at

constant

temperature.

Hence

equation

(13)

In i/A (9 \9PrJT=~R2
Subtracting two such equations we "Ai obtain

(14)
an equation for two phases,

31n^ _?fa
. 9P

V\ ?V2 RT

(15)

IV. The General Law of Fugacity.

a similarity which may be made more Equations (11) and (15) show a In equation (11) Q12^ the transformations. few simple striking by
heat absorbed in any reversible transformation of the substance from

the first
between

to the second
the second state ? ?

state
and

is equal
the ? first,

to the difference
multiplied by the

in entropy
absolute tem

perature

; that

is, ?^-

(Si

S2),

where

Si and S2 represent in equation

the entropy of the first and second states (11) and transposing the constant R, we

respectively.

Substituting
obtain,

9 R Tin fa 9T In equation
the equation -: (Si S2).

(16)

Jp

(15) R T
into the

is constant, and may be transposed, bringing

form,

9RT\ntl^ 9P
j , :?j ? l>2.

(17)

The symmetry of equations (16) and (17) with regard to the quan tities T and ? S on the one hand, and P and v on the other hand, is This similarity is peculiarly interesting in the light of the perfect.
brilliant theory of Helm, according to which two quantities are funda

mentally

connected with

each kind of energy, the one its intensity, the

60
other trical, its

PROCEEDINGS OF THE AMERICAN ACADEMY.

capacity.* Thus, for example, are pressure, considered the of surface to be tension, the elec

and potential, in energy concerned respectively volume,

temperature changes surface,

intensities are We

in which quantity

corresponding electricity, and

capacities entropy.

its capacity may denote in general the intensity of any energy by /and If we substitute / and H for T and S in equation (16) and for by H. Pand v in (17), the equations become identical except for the minus sign in (16). We are thus led to suspect the existence of a general equation of the form *
91

-Si

? ?,

and further, of the equation for a single phase,

This equation would mean

of energy intensities, /, P, In,

that if the fugacity is a function of a number

etc., the rate of change in the quantity

R Tlnij/,

with a change in one of the intensities alone, is equal to the

capacity. reaching that substance this to In other words, this every all equation, possibility cases by the if true, of the expresses change Let the of escaping various of us it embraces under

corresponding a law so far state examine tendency energies. of any

simple of the validity can be shown

conceivable all

conditions. in which intensities

be

for equation influenced

The
written,

influence of pressure

is given

in equation

(14), which may

be

and

therefore

conforms

to equation

(19).

* These of energy, and their have been hitherto called the factors quantities of energy to the quantity I believe has been written concerned. equal product is absolutely that this part of the theory by the facts, and that it has unjustified which shown to a conception has been been the chief cause of the hostility which a veritable boon in the pedagogical in research and has proved is valuable treat ment soon in another I hope to discuss this whole of energetics. paper in the light of the results of the present Meanwhile paper. especially as the dimensions and capacity of energy, speak of intensity signifying of energy. product has the dimensions question, we may that their

LEWIS.

-T- THE

LAW

OF

PHYSICO-CHEMICAL

CHANGE.

61

The

influence

of

temperature

is expressed

for

two

states

simultane

ously in equation (16), which conforms to equation (18) except for the minus sign. This slight difference might be explained away, but a much weightier difficulty confronts us when we attempt to split equation (16)
into two equations, each expressing the influence of temperature upon

the fugacity

for a single phase, /9R Tin

in the form, if,

\
This equation is in general
may this choose zero could be arbitrarily be chosen true, but of the

JT
zero of

.?
the fact that we
each temperature that the equa cases a tem either entropy. it could of fact and must be the the If for

not true, notwithstanding

so chosen

tion would determinate perature

arbitrarily as a matter the temperature, for all.

function must be

is entropy zero chosen conclude,

in all

for one

retained

We

therefore,

that the general equation (19) is false, or that entropy is not the capacity
dimension arbitrary that entropy of were has heat. it not been To that too make other hastily the latter conclusion lead the would also appear too considerations chosen as suspicion in question. In to the

capacity

fact, the equation, d Q = Td S,

process, corresponding to the

for the heat absorbed

equation for

in a reversible
of energy,

general

d E = Id H, is the only argument for the consideration of entropy as the capacity dimension of heat. This argument would apply equally well to any other quantity, h, such that d Q = ? Td h; in other words, It is interesting, therefore, to determine whether such that dh = ? d S. there is, in fact, a quantity which fulfils this condition and also the
condition

change

I9RTlni?;\

{?9T^)P
ments capacity The it may, of heat of I think, energy. every body is a very be accepted, at

= hleast as

<21>
the true

If a simple function can be found which

satisfies these two require

provisionally, function

entropy

complex

of

its

other

variables, and even

complicated equation,*

the entropy of a perfect gas is represented

by the

S=S0
* See Clausius,

CPln^-Rln^.
I. p. 214, third edition.

W?rmetheorie,

62
The above value

PROCEEDINGS OF THE AMERICAN ACADEMY.

of h for a perfect gas (21). = ij/ may For be a found perfect from gas, the second of to the the

conditions,

equation

according

definition

of fugacity,
P, and therefore

, - f9RTlnil,\ h {-Tr-1)P=
We

(9RTlnP\

n n = El?R

\-J?-)p
for the is consistent

^
of is.
the

see, therefore, that the value of h which satisfies the condition equation (21) is expressed by a far simpler function than entropy
Let other us see whether condition that, this value perfect gas with

dh=
For a perfect : gas the following

dS.
for isothermal change are

equations

familiar

,Q ? <?S =

dQ

Pdv
-^r-

=-?

vdP

=-?

RdP

z>j1
RdlnP,

and from equation (22), d h = R d InP9

hence, for constant temperature, dh = ? dS, (23) The value R InP satisfies both the above

and the condition

conditions every gas it for substance isothermally to will

is satisfied.

is easy

conditions

the perfect h in the case of a single state, Moreover, gas. of a perfect into the state of being is capable brought indefinite and Consequently expansion. by evaporation two of the either state of a substance that for any show the other with is consistent a value of h which define

condition.
the difference

Thus by the first condition, expressed

in value of h between two states of

now by equation (23),

a substance is equal to

the difference

in entropy and opposite in sign, that is,

? ?j_ h2 state may ? ? S2 the be Si. vapor regarded of the as a substance perfect at gas, such a

If we low

choose P2,

as

the that

second the vapor

pressure,

= h2 R

InP2, from equation (22), and the last two equations give, + RlnP2, (24) h1= S2-S1
of the entropy represents definition a furnishes complete S2 the of vapor at pressure of h for P2s any This state. the value

in which equation

Let

us see whether

this value

satisfies the other condition

of equation

(21).

LEWIS.

THE

LAW

OF

PHYSICO-CHEMICAL

CHANGE.

63

Equation

(16), namely,

9RT)n^
_fa ?

9T
holds which true for the two in the states state which of a is the vapor

Jp
we perfect

S2

Si, one of considered, just at the low pressure P2.

have gas

By

the aid of equation

(24) we may

therefore write

f9RTlnp
9T According to (22)

=?1-?lnP1.

and the last two equations \give by addition

which is equation (21). I think, therefore, that we

capacity dimension of heat, and

f9RTlnfa (9RTlnfa\

3T )rK
are justified
in considering

in considering
equation (21)

h the true
the special

form of equation (19) applied to heat energy. The replacement of entropy in general energy equations by the quantity h will have a
further latter, advantage the approximate by on account value that of the much may the case greater be in all of which simplicity cases of very the easily may

determined regarded becomes be

assuming as a perfect

the vapor of in which gas,

substance equation

in question (24)

evidently

= A
where molecule Q is and the p total is the heat vapor

+ ?lnp, (25)
in the evaporation of one gram

absorbed pressure.*

We

have now obtained equations of the form of (19) for two of the
approximate equation is a special form of a general and rigorously exact

* This equation,

= A ^in which when tesimal one \p is the escaping gram-molecule tendency is allowed of

+ ?lnft
the

(25a)
and Q' is the heat absorbed an infini its

substance

vapor demonstration

this Since pressure. be postponed. may

to evaporate will equation

irreversibly against not be used in this

paper

64 most
function consider and a

PROCEEDINGS OF THE AMERICAN ACADEMY. important kinds of energy.

of a a drop third of energy-intensity, liquid t. containing The change n

The

fugacity
gram-molecules in surface

is also known
tension. with of that the a drop

to be a
Let surface with has been us v a

namely,

surface

surface in

tension

change

its content

expressed

in gram-molecules,

is, -r?, dn

the molecular it by s. If the surface, and we may designate n a from to d is taken the and added drop quantity large mass of the the is of amount has, I work. The process liquid capable yielding called
think, always hitherto been written equal to tdcr, the change in surface

energy.
not in

This

is not strictly true.

to but There

The molecular
less always than

volume

in the drop is
volume of work ?

equal exactly the large mass.

always slightly is therefore

the molecular amount

a small

done against the atmosphere, and the total work capable of being done by
the where transference dv0 of d n gram-molecules the increase represents in the volume of is equal in the If volume the to td & of transfer the -f P (d v0 d v), dv large mass, reversi be made

the decrease

the drop.

bly in any way the total amount of work obtained must

above. The transfer may be actually carried out

be equal to the
as follows :

reversibly

Let a solvent be chosen in which the liquid in question is so slightly soluble that the solution may be regarded as an ideal one. The drop * with the solution at and the large mass of liquid will be in equilibrium
two different osmotic pressures, II and no, respectively. We may now

take the following steps reversibly: (1) dn gram-molecules of the drop dissolve into its saturated solution, (2) the same amount is diluted to the
osmotic pressure II0, and (3) passes out of solution into the large mass.

The
osmotic

three steps yield the following

the volumes no and occupied II, W1 = pressures

amounts of work,
by the amount d n

in which d vj and
in solution at the

d vf represent

respectively. Udvr Pdv,

= W22

dnRTln^~, n0

Wz=.Pdv.-TL0dvJ.

The
above,

sum of these terms, written

gives order not by

equal to the amount

of work

given

* In from phase.

the solvent

be of the drop, it may tension the surface to affect its own vapor and thus pass into solution through

separated the vapor

LEWIS.

THE

LAW

OF

PHYSICO-CHEMICAL

CHANGE.

65

P(dv0

dv) +

I?dvl-II0dv0f+

= dnRTln^tdo- + P(dv0 ? dv). II d vf,

Now
and,

from equation (2),

as on page 55,

no d vj =

Ko~~fa

Therefore

RTln^
This
constant

=
fa
If

t^ dn

= vts.

(26)
we

is the general equation connecting fugacity and surface tension at

temperature and pressure. t is variable may differentiate,

fa and s being constant, obtaining dR Tlnil/=zsdt,

or expressing the constancy of T and P,

(SJ^)?...=<
This equation completely confirms the validity of equation (19) as applied to surface energy and corresponds to equations (20) and (21). An important form of energy which we have not yet discussed is
electrical tricity. If energy, these whose be dimensions represented by are and of potential, quantity it and in e, respectively, any elec case

where
have

the fugacity
the equation,

is influenced by the electrical

potential, we

should

f9RT\n?\
There
shown

are in fact a number of cases in which

to have an effect upon the escaping tendency,

the potential may

the most important

be

being that in which

following dynamically ions form equation is shown an ideal

the potential
has been to be amply

influences the fugacity of the ions. The

and experimentally, on the assumption thermo that the

proved exact rigorously

solution.

tt= R Tlnli

+ K,

in which 7T is the potential at which equilibrium is established between an electrode and its ions at the osmotic pressure II, if c is the charge of
one istic gram-ion constant and K of ? the is at constant In temperature other words, and II pressure is the a character pressure electrode. osmotic

of the ions which will be in equilibrium with

vol. xxxvii. 5

the electrode when

the

66
potential osmotic from

PROCEEDINGS OF THE AMERICAN ACADEMY.

tt is established. pressure Since we to and are the discussing fugacity of an ideal the solution That this is,

equation

is proportional = p II, if/ (8),

ions.

eir=:RTlnil,
Differentiating equation, at constant

? R TlnP
and

+ K
pressure we obtain the

temperature

19 RTlnxf; is equation (28). Equations (20), (21), (27), and (28) comprise all cases in which to depend upon the intensity of any form of energy. is known fugacity The identity of these equations with equation (19) gives the highest degree of probability to the supposition that the latter equation expresses
an exact law of nature this state and one possessing expresses simple such the others ceivable possess. change to For of equation of any universality condition for Moreover, as any it will few con be

which

9^

y t,p,...

substance.

shown in the paper which

applies in the

is to follow this, that equation

(19) not only

a substances but, with simple chemically slight generalization to mixtures as of the which it contains, applies symbols meaning not merely to that it and further but also processes applies physical well, so that this law becomes the to all chemical law of processes,* general physico-chemical it will Finally, R T In i/f, which in the obstacles which Ostwald, section already and of this change. be shown possess search that such for the the of the two will functions remove

adoption

\jj and many in of last

peculiar fundamental has been

importance, made

so much of other paper a

progress

of principles the work by therefore of fugacity offer as

energetics, of Helm, in a the

I shall investigators. further explanation

tangible,

physical

quantity. V.
The Fugacity is determined for of Imperfect for many all. Moreover Gases. substances the and fugacity of capable of a sub

The direct * In

vapor or

pressure

indirect the

determination

will be seen between of this theory, analogy extension further the as used by of chemical and the reaction of tendency driving fugacity conception T. W. Kichards 35, 471; Jour. Phys. Chem., 4, 385 (1900)). (These Proceedings, I owe to the many conversations full of assist to recall how much It is a pleasure I had with Professor which Richards the early ance and encouragement during or escaping of the theory of fugacity tendency. development

LEWIS.?THE

LAW

OF

PHYSICO-CHEMICAL

CHANGE.

67

stance is the same as that of the vapor

important fugacity therefore of any gas to know or vapor what and relation its pressure.

in equilibrium with
exists in general

it.

It is
the

between

Figure

3.

If a section of the isothermal of any vapor is plotted on the P V dia gram (Figure 3) we obtain a curve such as M W, which, according to the third law stated in the introduction, approaches asymptotically the
hyperbola N N', whose equation Pv Let us determine the value of = is, RT. any point M of the curve. The

if/ for

variation
for constant

of \\r with P
temperature,

is given by equation (20), which may be written

dRTlni?/ = vdP.

Between

the two points M and M' we find by integration

RTln^- = fMvdP. Y J M
if the lines of constant pressure L M N and L' M; N' are drawn, Now /w I v dP is equal to the area M M' L; L, and this is equal to the area ? M

68 LNN'U R Tin?, P

PROCEEDINGS OF THE AMERICAN ACADEMY. minus the area M Mf W N. The former area is equal to

and if the latter be designated by A we have the equation,

RTln?

= RTln^-A.

(29)

Now if the point W is moved in the direction of greater volume, equa tion (29) holds true continuously, and therefore is true if M' is taken at infinite volume. But at infinite volume y
and therefore

p>,

(30) RTlnP-A?, if A^ represents the total area bounded by the line M N and the curves M M' and N W, each produced to infinity. This equation may be
written,

R Tlnil,

S TIn t
where The e is the deviation upon M M' base

-A?,

or In? = -^,
logarithms. from case is of the that course

or ^ = Pf?,

(31 a)

of natural of the area

dependent the curve

the lies

fugacity . The A N N'

gas has

pressure been

is, chosen

therefore, in which one. For

within

the

common

gases of the opposite type, hydrogen and helium, R

We and these any done a gas method obtained another value see at once the

the formulae will be, (31b)

vapors the value except gas of hydrogen ; for at be

TlnJ5
that for

= + A,
all known

and^

= Pe*r
and than the the

helium two,

greater. involves pressure by integrating the the

escaping The the

tendency determination estimation exact

is

gases less of of

pressure the fugacity must This

the most pressure

empirical

between has may form obtained

in question of by all using

A^. of the isotherm of equation zero. This the pressure and but empirical results the true the value equation coincide value thus of the of A^.

area

disadvantage be checked

extrapolation, a second If be very the two near

and will

recalculating An. in all probability

In conclusion
isothermal of use. liquid For along of all

it may be remarked
substances, not

that equation
to gases, and

(29) applies
can be from from

to the
to

merely to pass if it is possible example, that it is evident an isothermal,

frequently vapor

continuously in passing

a saturated

vapor to its liquid,

LEWIS.

THE

LAW = x?;

OF

PHYSICO-CHEMICAL

CHANGE.

69

i//,

and P=Pf

in equation
must constant of Maxwell. equal

(29).
zero. P

Therefore
That must is, the be

the total area A

two equal. areas This on the is

reckoned
two sides

algebraically
of the line of principle

pressure

the well-known

Summary.

(1) The equation of Clausius for vapor pressure is simplified. (2) The meaning and utility of a new quantity, the escaping tendency,
or fugacity, (3) The in are influence simple explained. of temperature and pressure upon fugacity is ex

pressed

equations.

(4) A
the change

simple, general
of state of any

equation, which
simple substance,

embraces every possibility

is proposed.

of and

(5) This
capacity

equation
of

rests upon
energy.

the conception

of the intensity

dimensions

(6) This equation is verified as applied to the influence of pressure on

fugacity.

(7) This equation is verified as applied to the influence of temperature,

if a new sion quantity, of heat. instead of entropy, is regarded as the capacity dimen

(8) This equation is verified for the influence of surface tension. (9) This equation is verified for the influence of electrical potential. (10) A method is offered by which the fugacity may be found from
the vapor pressure.