CHENISTRY

HsSTGNMENT
PHYSTCAL CHEMTSTRY
ORTC PHASE RLE

- KARTHIk.V

SMI90aS?
Sem
CBFN
CONTENTS
NTRODUC TTON
DEGREE OF FREEp
PHASE, CoMPoNENT AND
PHASE RoLE DERIvATION
OE CoMPONENT SysTEM
T e Sulpua Sy stem

Two CoMPONENT SySTEM

Znc- Cadium Sy stem

*Potacsium Todide - Wodte Sy sber

Magne nesium -
Zhe Systen
FexH.c ddoide- Wabea System

FREEZTNG MIXTUegS
RERERE NCES.
LNTRODUCTTON
The phase Kule :s impontan b gehehal:za bion

dealinq He ebavo u of hete «og eneous SS ern S. Ln

eheal 7may be
be Said t i e applicabion of
may
pha se Kule it s poss:le to p uedict
qalbabvely
ManS of adiag
diag nam e efect on eng?ng pMe SSu ha

temptata s-e and co hcehtsiation on ahebexog eneo us

Stem in eq u bum, s kelakion ship a-S finst

184 HmeHican phy sicst

iscovened aS
eatly as
by
W:0i and Gi bbs.

Hs a le be stuted malke matjallys

S
ma

F C- P +a

F e umee of degkees of feedom

whese s

and P is te
Cis numben of Components

of System. e tetms
numbt of phases
and
degwee of ieedom involucd in He
pase', Cmponent',

Stoetament F PhaSe Kule have a Specta Sigtianre

and cdea undebs tanding of Kase

ase S

essentia0.
 be defined as
PHASE A phas ma be cny hoogehta
hauing al phys ca? and denical
pay6 of a System having
He Eoroug houb A System ay ConSicb
PMopesetiec Same

one h a Se noe tan Dhe pkases.

A Sy
Sy stem Containin9 only ligui d Lwates is One pha se o

I-phace eystn lP=1).

Sy ster containng iqud wates andtates vaounla g i s
a G0phase - pha & Systen (p-)
and so ice
vapou
wortes, ate
3) Asystm onta'nng iquid
e pka st 0
pkase Systtm.
cale d
A System Consistin of One phaSe on
geneous Sy Stem
s alled a
con S sting of LoO D oMe pha s e s
A
he tesogereou s ysbe

ule euation slonds

systtn Cinte phase
COMPONEAJTS A
humbes of Components of a Systam in equili asum

Th e defined as ; " eas& rumben

rsem ompohenb ma
may
consituents tems of id ta
of inde pendenb ehemi cal in

Com po Sition 0f eveky pha se cenbe expne sSed by meanS

oF
oF a emical q,ua bion,
 DeGREES QF FREEDOM-
Te tem
teum Degke e of Fuee don 9epte Pnted
F R pha se Rule eqn aton Ce- C- s defned s,
by in

st e
Qea st numbesi of vai able fecb s oLid mu

So aG e Vaabe a Fied autumabrol

SpeciAed emaining
maining
s

ahd conple bly defined.

A System wR F-0 i khoan aS honvav.ant having

ho degiee of foreedom
Sysbem : F s aS wivan:ant having
fseedom.
On
deg vee of

A F-a kon ivauian t

Syste s

tzso freed om.

degee of
PHASE ROLE DERT VATTON
G:bbs rule ues e Cibbs- Duhem
gteaty on

eauation, whid is C tund amentd bass fo Ee uno nami CS.

TLe Cibbs -
Dukem cquabon cdas:ies H clarion thip betoen

pHe SsuRe (P), tempeoatune (T) and potenbi al fon chenieod tomponests
Ths c quation s
sfolloos
C Vdp- Sst tEN;syt
9uole is Fo ndesstan d
Houseves, a Simple way b desive phase
Compo Sb'on of ea phase is defined as Plc-).

Tu
hu S,
S to 6ad numbe of Vasiables caa
Pc-) +a
Numbes of eqwl:bnium ach phase s P-I.
fo eack Componen t's
No fon Cnunbe f Componen ts, number of equi ltilsum = PCc-)

To bal kumben f e t l:bria E = c(p-a)-

Nou, onSideHing e 0,
F P Co-b+a -

[c te-
F CPP4a- CP+c)

F C-P+a
 THE SOLPHOR SYSTEM

S a one o mponen t, fous- phase systtm.

phaSts
aTa solid fotns
p lymanpie
Rhambte sulhu(Sa)
MonsclineSulphun (S)
Sulphu Ligud (s)
cSulhun Vapoun(.
A te toun pha Se Con be He
phe Snted by only
ehem cal individual 'sulghus' :tself crdhece Ohe Com poncn6

of System
 TLe bo Csey stalline fbxns of sulphun Se amd Sm iib:t
enanblo tsopy R an Sihon oint at 95.6 c. eelou Ris

tempeatusre SR is stn b l e , whle obove S Sm is Ttoble Vaie

At 4S.G c cack can e ghadualy 6nn S omed He oHen

are in qulibsum. Ab I30 C, S e s . TLus
95.61 S 20
Se S
The C HVe S
A8, Bc, Co, BE, CE , EG divi des ntoH axeas.
* The ee aiple points 8,c,E.
aHeaS aHe

A 8G rawkedsol:d honbie
BEC masked solid Monoclinic
GE CD nanke d lnu Sulphun'
A BCD masked
Sulphun vapou
Cuve A8, e Vapou pke ssuke Cuve of
Se
* Cuhve BC, #e Vapbu pte ssusre CuVe of SM
Cuve Co, e Vap ou pHe SSuhe Cuve of SL
Guue BE, He bhansbion CuHye

auue CE, He fusion CuRve of Sy

CuHV EG, e fuston Cuve oF

SR
Eadh of SystensSR, Sn, S and S ae
biva9iont,
F-C-P+3
I-1+Fa
F
 TwO COMPONENT
SySTEMS CINC(AOMTUM STEM.

This CLn
exampke of a
etaletal Systm
i eutecic.
CuHve AO; he Fre zng point of
Cuve Zine (4in'c)
Guve B0
xeezing point CaGAVe of Cadnium (3arc)
Te Eutecbie point . Te Cuves o and Bo het at 0.

HeHe Solid zinc, Sol:d Cadmium and Soluion aHe

Te pint S Cales Be cuteckc He

pont on d

tem pehatuse 30 nd eubechic cohpo sibion is 837

Cadmium 7/
 Conponents inc and ad
Te Aea above AO, bok He admiumn
Compo Si kion.
a Ke
pe Senb ac iqud solu ion vayi
hbn0g ent ous
Con Sti tutes
L oluhon of tuo neta0s tng one

ha se ony. T s, He Sy Sbem te p 9te sente

d by anen cbove Ao

S
bivasont.
F= C- P+I -
3-1+| 2
TLe Ascea
e a aboVe 80, zinc and Cadnium exist as
liquid solubon
Te Solution, kegandde ss oP ibs Com pos iti on, te peants

Ohe
phase nly. Tus Sbenin b ove 80 S

bivasnant.
F C-P+1 = 2-1+1
Te effec of ooCing Lf so sion Sn e a9rea cbove

AD
Ad s Coled, zinc cprnatas as e 9ve selt is

Reahed. This onbinues e point ahen He Solid

eutrekie mixtuse (37 Ca + IF/ Z.) sepaxates. As clea

tom diagnan, te area belou e CLuve o Hepre Sents

ZinC Cund soution, a s e a belou Bo shS cadmiu an d

Sobution. Da belo e eutechi c enpesatue 9epe Sanbs

He System solidzinc Solid Cadmiun

 roTASSTOM LODLDE - WATER SSTEM

I has fou phases i) S.id KT, ) Suto

o KT in
kTin abt Jce and iv) Vapbu. Dnly 0 emi cal
Consbi buen ts KT ad o belng heCe sauy 6o depict CompoSibion

fal fou pha st S, i s a copohenb Systtm

o-co

Condi bions t exi stnce of vaiou s pha Ses

Since e
9e S uditd ab amopher ic pie isuue t vapo u phase is
7here

Ki-H,0 s 91gande d aS Conden Se Systm

syse
cmoorins Coh Stant, tao vasiableS, bempenabuse
PRess une beinq
n d Concen bhation : e Con Sde se d.
 TLe iutve Ao, K feeting poiat
point Cusve of
atr T
of falls
CAVe Ho shous Ht Uing Point Poinb
ce
Ly
ad dibi on soid KI.

The Cuve Bo e Solub:hly Cu1 e of KT. A4 0, e

Soution s wit
K. TLus He Uu9tve de picks
Saturated
e fect He Conten b9ica bon of Satunatd
of tepesatuse On

Solubro Souwbt0ity of K.

Te Eute chc 0. He e e Soution beconeS

poinis
Satunated w:R KT nd Re solld KKT appeans
a S He

Had phase
aee a above Ao B, He pe Snbs Single ph se Syse
'ssution'. Aplying phase ule enuation

F C-P+

a ea
eHea belou AO Shos te exi stnce o of SreeiC an d

Sou bion, wh:le asea Lelo 0 depicts re sente of

Soli d KT Cnd soubion. Belou e cute chie tempsebne

nt Re He Con exi S t i c e Ond solid KT only

THE
TR MAGNE SOMZNc SrSTEM

hick
is a typical - Component system
invo kues e foxmaben f an intesmeta0hc Co pound Mg
g Zn

T has ou phases Said magntSium (M), S»l:d ainc[n),

Soli MaZn2 Ond B aud Soubon of Mq and
and

made of ttao Sinple eubecbi c diagians.

ppeas
Te one ouasd lefepresents E eteckic sym

Mg- MgZ w:le e one ighb e ystem

ystem

Tn-Mg Ta
 Te Cu veS AC, CDDE and BE; AC S
Re
fczin9 point
fczihg
Cu ve ot inc
Cunve oF
agne Sim BE is feezing po
and CDE at f e coo und

pmagre Sium (6Si

*TLe AC t me lbing o'nt o
S lo w ered addikon f z'n C.
on e
Concenth aton ob zin c
Te RnceaSe
CunUe CD sko S
oF tempe a bu*e.
in nel 1iSe

Te Cu v e BE cehbibs Hat Re meing Point fzine (+a)

teaded.
faWs o:R Pe add:on of nagne
Sium until pointEis
e a0e
Along e Ac, CDE and BE, we

feezing point es

phese and oes

610 pkases i equlban V2 ohe

phase. Ayplying eHeduced phase tele aio

=C- P+ =
a- +I L
ab HRe ysem Mg/bad, 2./Gigad and Mg2
sho us

al mohd Vatiant.
:q,ud
Cand E. e systenS a Ke oabs
* Eutecie points
Cand E hav tuo Com ponen bs d
Hae
Kaee phast n

eq,ut ib uiumi.

C So MgMg, soli Mgng, lizuid

E Sid Zn, solid Mg iquid

 THE FERRLC -CALORIDE WATER SySTEM

This pxovides CKonmple of a - anontn b

sttm co ound s Gydnatesaeeuned. T
Com p i t
S sysbe hade f Seve a Sinple eu be ck c

Systans Sewen- phase ohdenSed systen. Fesxs eoside

c
(Fe,)\
tos hux stable y staLline hyduates :

FeCl.13i,0, Fe Cl*
*4,°, FeCl SA,0, Fe, HO
e ote n
olte oee pha Ses nvolue d ice, anhydbvous fen:c

cDon:de ans Saltion As k Como Sihiorn of aU Ee seven

pha Ses CCn be 9-1e pre Sen ted y Ëa Con sibuents Fl nd

tuw o Co 0 net
Te Cu
AB hows
ShowGS
Hab . owt in of
o fe eZing
Fve ezing

Poin dVetride a Lence s

add: ion
hame aS ofwa beu.
feezing int CuVe

We havalbng e Cu e
Bco, Fez Clc . 12H20 ad satsate

Soution n equulibnium a0on H:s Cu nve whds, erefhe

ca e d
solubbhy cure f ded ecaby diate.

uut ve OEF 1s s» bilhy wve of he ptahydoate.

Alng e Cutve A8, BcD, DEF, FGH, HTS «»d SK, ne al

pha se and ohe gpid (cluton) place ase qu:lbsiun.

*ktfke, arry*g e duced ha se ole eajabon,

F =
C-P+I =
a a+1
Hence Ke
Sysbens ice solutron, 1 a /tion, +H2o/ sol tron,
SH20/ colubitn, hH0/sbitn, F<0./ ssuben *erne sented
Van: o uS
ahe o h OVani an 6.

Te Eubeckc potske sre ae 8, D, F, H J5.

ta f e se eutkic oints te has ee

Sysen
pha ses and to comonenbs. APpkyag hduced phase wle,
f- C -P +i a-3t1:
Syste s noh-Vani ant
FREEZING MoXTURE
Combinakion f Substontes Rat when

med Lo use e empenats»e of mix tue

me linghtat n Re hea b of solubon

a.lb saing melng
o e Sy Stem s Components, wkidh can be Lqu'd, s.lid
bok. To akain suae st possble tempthatue, e

Com pontnts f mixtue ate used in q,uanbi ties

Rat CHyohydate.Watei, ?ce, Shoo, and vaious

Salks ond acids mix ues at abta'n

w fåt fueezing

d:0abe acid olutions awe

Les
tepdabusa o ot50'C. Salks in
teyeietuses 0 e Ran
an Salbs en wateh souion

Subsitutbon Cushed ce fos untes naks PcIle

în ad bion ab soling
arainlouoeu bempehatusee beau se,
htab of Ssubion of Re salb, e mxkae absonb

mekingheat of e te.
tte

buses f dy e and adeohdl s 0 ees Can

Fteezin8 nix

Head tmpenasn f-g0 C.

in e labonatocy u
bue S aseR uSe hanly
Fheezin mix

tempnatuses.
Jehe abe and mqintain o
 Tdstal Kequibement s
foo o Lo mpera tu r e s 04 fulbLes|
f cev shed :ee and
by freeing akuoe at Contan

9eag ent DaCO,

gade tele sQlt, o

REFERENCES
* CHAPrER - THE PHASE RULE
uo9ea Applicabion.
* Wikipedia 6 Oefinitons