aans ot
ous predurR ntermchans amona
Fign enmperotwn and
moleeulen in mivxluren of2ae) aro nglecded ncal
ut hove aana
bohavea uke ideal 20901- all mixtute e
thertmodynamie proporcthon
lemporohum T- at
Pura hqud A in eloed comainon
delocminad by he magnirhude
Tka rade of evaporation o(a the
botucon ho adamg of A a
bord
of teenory oftha
erngy
Aupdaea of he qud
e mumbgt of adoma in the
rodeof cmdonsaiqn in
strike lhe aurtaes of tha liquid
Naipour phone which
unu ima
R equutrksuum
onkP
A equltuur ea)
eCA)kP
aro enpaertial
(Te aaturaled apour promuen of qunda
funehian of demperatuca
kept
f pur iqud B in eloned eomdainon
B contaimna a amal amaun of A:
16Xk
A eamlaioin a ma amount of 8 Pa Xn®P
Rooul'alaw
hvapourt exercted by
prODuraComporart i
6f i
on 1
noluion
nolui cqual Jo lhe produet of Hha mole fiaetton
in he nolution and the oturalod vapoust premune of pun
liquid al the emporadur0 of tho olution
poun presyurA
i deal
Parhol propcrtias
Tha trormocynome propertho had compona rh hovc
in nolution are called parctial proporthen
Gribbs- Dunem ecuation:
led Z be an extensive unchon ke V. SG
o 0na mole oluhom cowLh na o mo of Cmpononks-
and Z bo he0m ptoperty or any anbtmary Om ourd
solurion ho thad
1 a urehon of demperatura, pmemur ond cmpoition
, Ya)
Parthal molart volua of Z, (2 in inera0nR in 42 uku
1 mou of t in addod to h
d7 6 Z, dn; + 7, dn, +
47,dn
Sine 7 7, arte
charge of z fo mole addin
of Componant 1, 2, a Aoluhon have , molon of
componont 1 Tnoln of Componant 2
Z 0Z, +n2 +
D,fenentiaing eyuion -
dz n,dZ, +nd7,4 ....
. 4nndZa +Z,da,+ Zdnt
.+4}, dn, -. (io)
Frtom equaion ( nd i-
n, dz, to d7, 4 -...+ nndZn 0 -)
didin equaion (u) yn
Xr d~0
4
For a
binory ystem A-B:
Xn dSn +Xg dp 0 Xpdoty+Xg dox =O
Relation betucen tho molart Gilbs aco
nd uthon cnry oo a
and ha parchial molon Gubhs
the ee ne o
[Link] of tw noluhion:
ANrdnaeepQukem equakian unpiraty naA-B),
For bingry ao -B ad iod emp and pre
Diwidn asth idenbnatnge
Divdin ntnn, e
G- Xn G 4X. G )
[Link]
d
equahan )-
Xn dG tXa dGne +Gn dXA+ GaXB
Aecondinn Ho Gibbs Duham
equation-
Yn dn t X de -0
dt- G, dXn 4 Gg dXs -
(
Now
a+X =1
on dXA4 dAB -(0
dX dXB
dGGn dXn d -
Gg dXn faom equakon
d (
dXAG
,X
n, X, do
dXA XgGa X Gta Mulhi bsm adon by Xp
- ()
fquahn +Gi)
G + Xn d.
Sienboxly
4Xn do
Lle knaw thal
d t Vdp SaT
tor othtnmal ptoo-
dGt VdP
o, d dP pV-RTV
Imeaion tom 1ke ntandand atofe (-1ahr
on, Jdt RT 1
othe dre of indoreot? al constant T
, G-GRT [An],
on GG +RT nP
ushero G =molar rce oronay of an idul 20 in idn dandar
dde
molor Jrce enory o
an rdeul zm in fhe aade o
vgacty
unchon a ord of corecded promuro)
lugoeny a
wuch whan ued tho ncal paouka ontouren
in placo of
t i n Junction in
bohuxen G and ha Jeatithm
ivcardy
any
any nlade ony 3
e know ha
Gt G+ RTnf
RT
P
no ryical igoiconcof f
do- NdP - SJT Ngood
torn inolher mal proco-
dG VaP
V RT
On, dg -a ) df
,RTdlnf P
-«) do RT dtnf]
P-o
RTInf RT In - dP
, RT An fadP
P
b Acivny
Pura A A in solution
,RT An C ACC)
nCe)+RT In
wthlow Tupout prenunA-
ton aaubs tune
fP
h t + RT n )
actut, a uwhara n Hh commpomart in nol
ehonieal reation om, parcticular in
n most Cane
not hisn
yrtoma, Napout prehune no thal-
maallunieal
ihereiora
ACe) Are
tRT An (
O, bnco) RT An O
h larm h i s ha
molar dree entry of A in tha ao
wth tha eone whieh eorts tho vapourt pressurte of Thin
acm s ealled porchial mdor drree enoray of A and 1 denotod
H i s alno called
ehomical pdential ol A)
+RT no
G G ;
hppro mothon: pressura imtead ofaoy
Roou law: a X (uhun bokaven ideally
+RTAnX
duo
dua Ho
do ho
tht dormati on
eThe hange in Gibbs Iree eneray
Soluhon
Lo & candensed tate od
ioccusuna in
1 mol pura eompona won
whon oceuran
0eUr
and
Teuorts a dugaeity S
ho
ho tomperarune
dompenattura
TT 1 exertsa
extts a
ad tha
in a eondonsed ol
Jouwerc Jgaady
Now
6Gy;insoluion) G;(pura)
RTAn =
RTAn RTAna;
on, G,- G; RTAn
AG RTna;
molon of' A and ng moles of 8 aro mied do form
eomstat temporaturo and pressusca
o pol a
he ibes fice erry
betone mia naGnne
onary eaused by tho
hoo the
Phe chag
in he Gubbs
do a k terna
imiecnal Gabs
Gabbs ee
pOeoss AG'M
AG" redenred
m ing proecSS ithe ddfeconea borween thooe quahtias.
ofmii
ennay
t+ ng1n)
Gt ngG). (nnta -
DG" ,
RT n a + Dg RT naz
AGT RT (Ina, t+ngSnoe
M M
DG" X d6 +XG
and
AG RT (X, Ana,+ X, {nag)
HeohHead a dotrutian oon ide no
ha Gobb) Helmholtz equalion
ol
-
tor a eomponem in a
GH TS
S
onG/. San S doosnid vary uth omporahura)
(1/T) Jy, omp
Hacan-
GG RT na;
ROna)1
o1/T) , eon
H H =0
o A and
Fort a binary no" (mictura of mulea ns
oB
A H)+n, (He -He)
tmahon an ideol 'o i zer
Sorcmahon of an
The change volumoaeeompanyir Hhe
Wa know ha
do VdP -
Sdt
a, da-0 [dT 0))
9
No-
oP
Or (RT ina) VV
T, comp
V-V0
of ond m moe
OR binary ul"(mixBura o n molen
of B)
o, AV"7a (-V)t oVV)
tha Jurmohion of an
hecange in volum
accompunya
deal al" in zero
entropy o frmohon oan iceal ad:
Aeeordine o Gibbs Helmholtz equahion.
Gt= H- to TS
S
P, eomp
ideal Dol"
A ca a
RT(XALnXa +XE InX,)
Henes,
As R(XAn Xn. +Xn nXa)
ideal binary ol 10
of donmation of.
an
The entropy
imdependet oemperuhusa.
Non-idoal so
A nm-ideal sois o in which ha aclivdies c
arta nd equol thaure mole ractons
e Components
Acividy cocHcont
he actvtdy eoeheert of egmpanent of a nol"
definad a» te raho of eachvily of te comparot to
i
mole rochion i.e, on he componert
Y,
Fon a bnary sol" A-8
borueen
The
Tha abracive ineas A - B A-A ond B-B ar Dama.
Tis in onof ideal no.
the endition
Postive deviation means tha net atroctive dores botueen
fore behueen A-A and B-B
A-B in lem han attroetive
and id in tha opposite o nogative deviatan
Y1 Posthe deviahon
Y:1 Neaathive deviation
The achvdy cocsfiéiet Y is a Sunehon of tompercatu
Yvoruos wth omyorcahura, hen AA" ha non-
Zeto voluua
non-idcal ao
tor non-idca no-
OG"G RT Ana;
RT An X )
-RT(IM 4 Ini)
No
G- H-TS
n, -S
(&/T)
o1/)
on AH" iR(n r, + InX)
o(1/T)
ort AH aR InX)
o(1/7)
oCRnr)
(1/T)
In eneal,
eneral inercqosiny he 4omp. of anon-ideal ono
causes a deerease in ho codent do uwhich 'emporents
deviote rom idcal ehavioun, i0,-
cauen Y: to dkeras
Tf Y71, an Inereone temperatur
dowands umty
tormperatura eauwe Y to inereae
Y1, an 1nereohe in
ouanda unrty.
om A-B binony syotem occum whon
hoharmC mIn
in nugotive han both ho A-A and
he A-B bond oray
bond ru mor
- 3 bond erorenx ond Caner a andency doward omdeur
in Hhaol in which
which he A odoms tempt o only hove8
adons n naotnaignbu and ia-Vrtndxothoqmic miAlng
hun iwcieade o endeney ouandthe ocmotion o a empounc
between he wD Componants.
OceuRA whn tho 0-B bod
bord endY
enuay
Endolhormie miu
the A-A and B-B band entrgion
i l o n nivo thon bo
owond phase eperodion ot
Ond
and n causos a lenceney
in lha The A akoa atdemp o be
eushorun
elunerung
and the B oton alempt to
co-ondinadod only by A tonwa
dm.
ba Co-ordinadod by omly
ehonze o iee entray wilh lemperat ur alwaya
ohve aloge
Accordir
Hecordirg t teos- Helmhotz cquahon
G H-TS
on,
The ehar
The change of nee encry ih empcrahura alway has a
negahve lope
The activity cf a poeion is unity whon i al th
tcandandatae:
,0
A ntandand nate-
on, P A
CirRienpective o tha ehoieo of tho ddandand do)
npacion A bohavon dcolly in the hole compoantion
conge ofA-B binaty sol", 1h ope@ion B adobehavon ideally
Aecookng o Gulbs-Duhan equabhon-
Xd G+Xg dog -0
on, Xa d +Xgdo0
on, X RT din on + XRT dinag T:NGr-. RTdtn a
m Xd An ag tXg d Inag= 0 -.
As A identbokaven idealy-
dX. - d on, dXatdXe-0
o d man =dn Xa A . dXa= - dXa
13
Xndnda O
On
o- dXe + Xndin o0g O
0 dnas
v d Inag dnXe
na nXte
X1, Og1
Inag n An
Bpeecn aho behaues ideally. [Proved
delormnaia
in aetivity
9 Application Grlkbs-Duhom relationship
Aecorcing o tha Cobbs-Dukom equation-
A-B nol and UBin
Applaed do a binoty
ha exdenahva pTopedy
X d G + X dog = O e
=0 aa dGr, RTina,)
o dinaa+X dindg
A
d lon
of awth empositHan inknousr, than
1 thavariehon tha valuo
valuo
of equation dicom XA =1 do Xn Tetha
Intoration
at n
of log4A
:1
This cquadion con be ohcd. yztaphica inearcdion aa ahaun
bolo
shatnd
ahaded o0a
nde Can evauato
XA
(As X1, a1, ln a 0 and n 00; huw the eurve
oxkibits a l l lo ininty X 1
As Xp0, Ap0, In og and 00 Thun the
eurtve cxhibits tail Jo minua iiuty an X0
Ofthene
hose fwo pons. powd 2 is inuobed in to he
ealculaionm. 1itrodueoa ROUD uneetkiudy 10 ealeulutng
eon be avolded by comidorung oefhvidy
oeicientntoad o actiuity
YX1
on dXa 4dXp O
eÁD he
Xn dnXa XrdinX O-i
Equcin ) (6).
Ynd In)4 Xndtn a 0
on, Xn din ya Xediny = O
oP dOny
YAln
Thun,if the cmposthon knoan
variadon 6 Y h than
t Nalus of nya
inyrgion oequotim i)ca
eomposhan n a
Iny
X1
phaded oea X
- leY
WHh hin mhod, i n possible to accurcdcly evgluaie
undor cure d e 1aluwayn nite
he 0
aunction:
have introdund a ot Junction
Danken ond uury
calledfunction o eliminato ha 2d tail do innity-
ny
1-a)
Fo A-B binary ystem-
o n g'
bdh ido of equahion (i)-
decenthna
diny 2Xa dk» +Xa da
a diny d i n y , = - 2Xa dXa- *nXg dg
AA
ny -
2 XpogdXA do,
Y
Now
ny 2 XgM,dYh -|d (Mala a) +o,da)
2 Mai dXa- Xkae+,Xad
Xala 2X-Xs+Ya) o,d
- XXRa
Relahonthip betueen Hentyn and Raoulbo n low:
Henny'
Henry'h law on ha nolude. B in a
binany A-B
so
Og kXg
on, AnOg =
Inkg
nXu +
n no dink+ dln
on dnn dinXa [dink, COnyland
isertig ta indo Gihs- Duhem equohion -
din a din X
XdXe dXe d-din
dx,
17
dn On dinXa
Ino- nXa to Inc
ACOvrand XXa
Bub dolination, a; 1, 1Ond hwn e inmerurhion
enstand equal umiry e rcone of emponhon
Conwquenly, 'in
oyer which h lude B obey Honny'h lau ho aluend A
obeys Raoult la
TbhExeos Sonetin:
baucen o
Hin doinad aa the dkonone
horamodynomie funchion or neal nol" and Thorcmodynamie
unchon Jon no ssumtd do alid.
M
G
RoalRT (XaIna, +Ag mag)
RT (XR n Xn +Xg n Xe)
Xn Inaat Xg Inag) RT ØGIn aXp AnXg)
RT Jn+XnX
pRT (X» ny, 4+XnIny)
Kepudon sol
ue have tuo eaAeelassed o o
6) Tdoal 0 X
Av" 0
- RX; InXi
Non- ideal ; X:
Reqular o in nomathing inbtween whone dereneo ot
entralpy of m is nd not ecual do 7eo oud Chan'
bu char o
enlhalry D am
AS R(Xp nXa +Xg lnKa)
8G RT (Xa Nn XatXa InXg)
M 0
Cubbs Hlmhotz cquahon
OC - AH"- TAS"
idal Aol
TAS Du 0]
AG
DH TAS+TAS
For ulan Aal"
AS ASi
M
AG
OH TAS" + TAS4
b DH RT n y, 4 Xg In 7
d
tor eudar noluhion-
&G
G RT (A,a,X +Xg Xa")
RTaa Xp (Xa+ Xn)
AGS
0G RTa XnXa DH,
