Professional Documents
Culture Documents
CET
CET
CET
SbLUTIOn THERMODYNAMJC
0 lntensive Propertie
Do not depend mass ov mol (Independent b
Thermial canductvity vitcoiy
Eatensve froperties
9Vowme,, Swace Ar ea,
Depenod Dh
int ernel Cnergy Poterti at Cnerg
Eztensve propert
Dr u e
secije propcrty
a state Variables (br uncton)
state o the syte
Depend ony n the nalpeth
DDes not dpend on the elbwed.
E4 Iternal Encrgy. Ptental Energy anhapy
Patth Varinbles (by qun ctims)
achieve the cwrres
- Depend bn the path olooed to
state
Work
)
Ehtrepy
dU= d a t d
dU Tas Pdv
Enthalpy (H)
dHdUt Pdy + Vdf
6) Helmholte Eneg ()
AU-TS
rentiating
dG Vdp-S dT
MAXwELL RELATIDnS
Let
M=
),
Eqns. to cen be repvecerted in the or t cq. )
ea. ( can be oritte
Eq
dH T s t VdP
S) (),
Eq. dA =-PdV - SdT
(2
() -B). B)
dG
- Mízture Rpex
where , ME Mb) ar Preperty Totel ADle
We
knowthat
irtre
Property
M' M(T, P, n)
dn
As
Substituting -
M;nd
ni
dT
P.ni Tini
& M M
Cquivaletly
ldeal aa iture
Rf
Partia volunMe V
FUGACITY
For
From eg; ,
RT dP
alenf)
RT
RT 5)
t oteI is
29
where, Fugacty Cogj ört
Residual Property :
Co wpressibi ity" Factor
V PV
RTlP RT
P
d (ln f) P
D bot sides
P
aive.
Calcn ate
fugacity At
-0- DD36 P
- D.bD3G XID-D, D3
D. 965
’ f
e D-835
f yi76
oata r Co t 23 .
25 o.999 - 4eyxI
Trap tioidal Rrde
-259x\p
2D
2482 62b5X|67
2:D819
(OP= 50 bkr
Ln P
P uOD b ar 2D6
1DO
25
2g
+
205
25
2
5b
2 (-4-14%64 23 59X\64)
2.
(-2-59x 16+ 9. &X165)
+
20
2 (9.g x16+ bo205 x164)
Liquids
@ Liqids with Mbderate vepor pvessre
Fur the state o vapor-liauid equi librium,
1gecity vapor is sane as vapor pressure
P, = vapor ipressure
As the qid is in eyillnun with the vapor
ot
'entiating
H
-
Ho-f
RT
UN 2.
# Binar Slutions
Partiat Preperties
Cnsder a binary selut'bn
h, = ADles
n, tles o conponet 2
Tot al woles
Mizture propertvn (ntn)v
(>v
’ M, dn,
dn:
Substit uting in eg
M
M, = M 2
As d -d
M = M+(1-)) 2M
Sub stitvirg
br b
M,
Siálary y Pure compunent2
M M,
Partioe Property ot tngihte atlutien (M)
Postiad property conpneat II ot injnte dil ton
eN aluated when the conenrabn ok other
compDnest s inf fhite
Numerical Dn Partal Property
tn-Se 2,022-23
q.2). Giyen.
Melau Erthalpy a binary soltien
Partil
Reoriting h
50D,t 1o00() + 50 l - ) + 40(l-2)
w.r,t,
Sub stituting
2-lD0 t50
Di46erertie
55D - (202 3b
Let
From eq.
- 601- 36)
540-.6Dx + 20
t 30
d' aP +2 dn
t constat T & P
(15)
This is aibks- Duhem Eq. (oginal torm).
2 chenical ptential speeiy
ndM
aivide by dn,
() dn, - dn,)
Cibbs- Duher t4
alse be
n er S Coegyicient
UNIT-3: VA9 0UR- LIQUID ERULIBRUM
2 t (c- ) P
Tot al nMnb r ln oependent Eqilibriun equtio
(p-)c
2 +(c-)P- (P-)c
s ubstittirg in
Minimun is
ve
mazimum is AG
ABE UNST is
Osystem phases (A the
tionb, dican 7iven nder
be
EquilibriwM
Syste ase Ph
Eqnilbrim Phase stabiuty
stituting
eyin Sut
free Gibb's
T,
Constant
P. . 3?case
e4..
sbstittingin
Lney HelmholB2
Free TS U- A
&V srat
T Con Case2
R aouts Law
a srlution eerts v apur pressre
(, -
Using Dal
al ton's
ton's Law, partia pressre in vapor
phese
P
3) There is Dr
Terupey ature chen9
B The coupnents tbey Raolt's Law.
La
End-Sen 2022
Griven: For a Benzne Toluene systenn
B
Antoine
cOpDnd A
, o 33 T= lo°c. Find
1 ’Bengene 2 9 Toluene
P 180.D5 kie
3103. o)
|u.oDg8 -
100t 219.73
2
2 4:18 kPa
usng e
|o9.12 Lfa
D.33 120
10912
P=
D. 33
From e. t
S
u39.741 17418
:.|T=o3.4°c
b. 33x 19722
4.)
120
where,
P Total pressre
éaz Vapor phae wol racion
Aeiviy cOnponent sol vtion is deined
Actu Portial Pyessure
1de al cse Prtil Pvessere
fUr a
Binry solutior in Vapor - Liquid cqilíbjm
Tot e pressuei
End Se 2022
I ’ c y ohenne 2 ben2ene
@.2@) Given :
P = 24.62 kPa
o.u O.
28
27 P
26
24 Du
O.2
b22
2 Phene
a2 Q2
Ala)
2
A(1 0.70LA
= A(
D294 A
b. D86 A
2
(D. y9g- D. o26) A
B1.(6
P
75.2
A-2")
d P
32.26 5.2
5,95
5.42
32·26
P= 38.22 La An
Azeotrope
Srecial CAeabrs c sol wtions with
wth sahie Concentran
bott varr And Qid hoe
to
282
hevity coagetent A2cots opic con ent t o
,
- ((-2y)
Dn both
Cerves
Chect
Both tte slopes
oppusite ígn
t condíion 3 is sDticed, subst5 tute the valuec
and he ct i LHS =RHS.
Gror owAplete test, rpeat steps and ) r
btaer values .
exhíbits Mainua
but
2 yom (2, sipn ir oppusite
At a particu ar
(en ) a
Win
nin
consisteot Inconsitest
using Dota at the Mia- Point
yE22 b5, Va Laer
L eq. be coMes
A
A , t 22) B
AB
B (At B)
2 BA2
B2 (A+ B)
A (
AB
(ABY
AB
Cnsíder otlowing
B A
AB
Consistent Ihconsistent
betocen intr
trtcgratia
rebreseot end stotes puwe conpenent.
hest
these pwe cOhpehent nd stotes
RT
eneous
Te
Brye
phae A- ch
phe
M
A
Te ine
AO B()
Tis is te
iuply equal solubi lty AC BC.
reason-he Tie ine RME oiL aayS
ave pDstve
s\ope. alays
Type-I
Pair A8 is partally soluble
bther 2 pirs AC RB Bc Dre soluble
A)D c(o)
Poimt 'p" is called Plait point - vepre septs the tot P
Aie ines ohere A-rich and Brich phases becone
denti cel
Ye-R Eqi ibn' DbAined
Tie nes.
9 Type-2 ystem
2 parys AB are partialy oluble
Dr y pair (Ac) is uisible.
c)
D Co) B)
Liquid
Solid vapor Gs
SVE
Tviple poirt
Te
Teupeyature
VLE ’ Vapor -Liquid EqLiibríum
LSE > Llaid soid
Eqiibrýuhy
svE > Solid -vaper Equilibriw
riple Point : The peint on PT aiaqy
o 2 phases (solid, quid, vapey ) eaist in equibrin
t 2) et the cuYyest State
tLe Laaterioe s soi,
represerted by the
Ahe point p
P.
the pesswre constont, toe w'te het the
eratNe
state
tinuoudly
thateri al
heat, the
Qnd t e
tehp
Reaction stoichioery
a cheuical Reaction
aA t bB cC t d D
is con be written al
-+d d
Chenial Reachion
Erample 0: consider the toooing
Reactur onti
GD kho) H
Atter SOMee
the number oles all 3 species at tis wwomert
2 H2
2Dkmo)
Ho reacted
-30
Consuwphtn fov wat
5 20
PYodu ct
Let A C2H
in al nnbey o moles in Product ere
nco
eapressivn can be wrtten a
qeneral
Drdinete
Reacior (Reacotn Co
can be calCeelate a
speies
nto
20 nco
-2
r2Do- 2E
120-2E
120-28
Multiple Reactions
Foy Reaiorn system, eq. O Con be hodi7iad
2)
Tot ee
el oital hMoles, 2 +
3Sc) no
2 + 2 Hao- cH-3D, o
2
2 t 2-|-3 D
Totod na ha oles, n
2
Using
2(2-E, - E)
2.- E,
Bo
Uol raction
3 E-3E
ol rachir {(c4,o
204 E)* 2 E
Yaction
2(0+ 2 E2)
rachion
2(0+ 2 E)
April 2022
2 hrol Methane n 3 we) waser
Q. G(0)
the oltowing veactior ?
Cot 3H
+ 2 H
Derive
Reactio.
Init haoles Dve
Let A’ CHut
3wol
ngo WAoles np
Tute 1nitid woles
Reatend be Loritten
Let Ead ent of Reacti on o(R)
Ph Reaction
| t 3 - 1-| 2
Mol raction t
Mol CHu
2 - E,-E2
5+ 2(e,t E)
Mol Yactien Heo
3-E2g
Mol ra ctior
5+ 2 (e,t E)
E2
Chemical Reaction Eqiibria
cheicad Reahon
K, cC RO
Lwher the reaotion attoins eAui Libri uht
Rote for ward Reacto Rate o Backipad Reacsonl
K Equili briu constort
The e t e t React'on et wit any reacion attaind
equilibriunt, is deter ined by K.
HigherAReach Att ai equibrilsha t oer E
Looer
Let Ea Extent Reachon at equilbiun
AE equbrileu
Eqiibriuy Constaot
e is dejned a 6
- f (a;)
K Ka =
a
where Acti
Stoichioetle n b r
we know that
RT d(enf:)
StodQrd stote to wrr state
RT
RT
Substthtng in
-(a
a a
a a
A a
2-RT K
)
Feasibilty ot aa Reacion
- AAcheical relcon oie tae pl ace nly h t is
therody nanically 7easible
Consider the decowepDsition water vapor
HD )
At 299 k , theequibrí wny cont
k 40
React
is not th r wodynaìcodly g'aib le.
we know
’ Rea ctien is FaupYable
’ Reachon proceeds to a conside -
Yable extet.
Less FRUoyable.
veations oith +ve Aa re ¡evorabe.
Gy6,2DD
Sthesis
reacion
ovF S Dend easíble,. This
caryied hagu presseres to byerCOMe
the whavorable
There elr degined deny Drcato to separate
is nD Loellr
1avoYable ano n qevoy able veacons,
criter ib
Rea ct bo
Reaon
At st andRyd state
H;
( G T2
St and rd He t React'on
Sub stitttrg in eq 9
)
Aivíde both sfdes by 'R
dT
d (ln K) RT2
Van't
dT
AH
R
where, Aaf tibbs EnergY change 4oraf
n T2
AH Products (T)
Reatants
&H°T) +
the Drm
K; t B T
Cpi
> Ev;qi 2 ;; t ;B; T
A ' t Ap T ohere
substi tutig in
)= AH° T) +t
AH° )+
bH°(T) + bd T 2
AH°) 2
where
+ 1
2
from ea. ,
AG - RT n
IRT
2
Constast.
where I intgration
Det 2022 d April 2022
Civer
Nz (q) t 3 H2 ) 2NHa
At 298 K,
Let
speies H2 NH2
27.27 29.75
351x I63 25.) | x63
At T700K AG and K.
Sal: Let Ng A,H B , NH 9c
Rea coh: A+3B 2c
Heat
AH (T,= 298K) 2 ; (AHi):
- 92200 JwDl
2 (-u6 t00) -
E ;(0G4);
2 (-t650) -33 oo0 Irol
t T = 298 K
using
NH'd)=
34-7eX 163 Q98
-g2200 SH'++ (-u8. R) (29&) + 2
922Db _ AH 2999
H
79201
vsing eq at
AH'- Aod Te T
21 D3 - 27757 I
33 DO0
at
+ I
-RT K
A6ect D P on K
L does nDt vRry coith .
caniibrn Constet (K)
ceUses change in
HoLOever, Change in Pressure
caiibri uw co MpDCDn.
K Ka
a a (a?)
A
F (; P
p pd
F(P) pb
1deal Ge
For
K= Ky P
K
UNIT-6
April2b23
@-7(a) iven: P |6D bar
Ka ||22x Ib*5
3
2
no
2 - l 3 +2 -2
3-3e 3(-s)
2 E
ne nco
2E
y- 2 2-E
-3
NOw.
Ky 2
2 (2
(2-E) 27(1-e)
16 eC2- )
(1- E4
using q ,
K
((-e)4
1122 o3 ((-e)
(2
2
4E) = 7X16 (1r 8)
1-22 xx16x (-e
((-) (o)22%to')
+tr22 (l-&)1
n A x|D
D.979
76) Let CO’ A H’B
Reacen
Wi t Mre A
Basis nitia ioles l we) A ol B
nA I,
Va-2,
B
Final woles
l- 2E
2(1- E)
2 (l-)
2
No, y 2.
2 x21-E)*
2 (- E)
(r2e)2
ASS Wne
p
Ky
(5
(1-2E)
25(1-2E) -
O.4
is fnvald as ng cannot be egetive.
1 ( X100
Final uoles
ng 2(1-e)
ne
E (3-2ey
K Ku p
3o96 t 10 D
1oys-212
A
Oct 2b22
Kp
Calcelatei
26 10028
A
60- 3E
Go3E
-3 1b0-2
H
2 &
2&
2
20
20
1DD2E
|o-28
-2
-3 2
27 (20-¬)1
(50-E) (56)
D. D)25
27 (20-E)1
16 E Go-) 3 .25
27 (eo-E
16 E2 1so-) 31.25 x27 (20 -e
BO
)
38
20
(bct 2D22)
T-29?K
iveni Czty t
H molk
220.8S 48986
-24)997
8912
-2389 4)
Equiisriny constarst ki
B HD
tet
298 (-31.9)66D294
Al so, RT
p2645 |4.37 As ba<o Feasible reaihin
April 2o22
’ C2 Hy t Cz He K, 3.8 56
Ke 262.4
CuHn- C3 He t CHy
Let E,- Etetet ot Reacho k)
E, Extent b1 Reaction R2
BASIS
n; nit ; E
)
B
--
E2/+ E, +8)
E2/+ E, + 8)
cHu
(2) -)
2
8-343 E
Ki
substtuting
3.856
&j)
(1- g.343 è) st3 )"2 ¬
56 l1+ 9. 343 E,)
6)
> 3-8 2
3856 (- 87. 29 E) l2 Ej
2
337.79 3.856
nd
Pvody et couposíHo :
D o531
April 2v22
T 2915 K
-l6.747
n 228.G
CzHsoH-74982
Nz t 3 H 2NHa
3349y
RT 2314 x 298.E
K7.37X o
187695 75 72
RT
32
K 7 6 7 Xib