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CHEMISTRY E182019
CH7
T-S diagrams
p=1000 bar
technically realizable maximum
T-s diagrams
Gas steam
Saturated vapour curve
Liquid
L+G
CH7
T-s diagrams
CH7
Solid-Liquid-Gas
p
Phase diagrams
L-liquid G-gas
p
S-solid L+G
S+G
T v The reason why the regions L+G, S+G appear in the p-v diagram is that the specific volume v (unlike T,p) varies during phase transformations.
CH7
Solid-Liquid-Gas
CRITICAL POINT
TRIPLE POINT
CH7
Solid-Liquid-Gas
Melting hSL>0, sSL>0, GSL=0, dp=dT=0
T During phase transitions the pressure and temperature are constant. Also Gibbs energy remains constant as follows from its definition g=h-Ts=0. Only specific volume increases or decreases.
CH7
T Phase transition lines in the p-T diagram are described by the Clausius Clapeyron equation Enthalpy of phase changes, e.g. hLG
dp h dT T v
CH7
T
The slope dp/dT is negative because specific volume of ice is greater than volume of liquid
Melting point temperature of ice decreases with pressure therefore ice under skates melts and forms a liquid film
CH7
Clausius Clapeyron equation can be derived from energy balance of a closed cycle in Ts diagram:
dp s h dT v T v
T+dT T
s=s-s
CH7
Clausius Clapeyron equation is exact, because follows from thermodynamic principles. Individual terms (dp/dT,v) can be approximated by semiempirical equations (different state equations, Antoines equation)
3000
2500
h[kJ/kg]
Antoines equation B ln p A C T
pv ''
RT M
2000
1500
hLG
RT 2 d ln p RT 2 B M dT M (C T ) 2
500
CH7
Multicomponent equilibrium
Binary mixture
Gaseous phase
y A=
A LIGHT
B HEAVY
Liquid phase
x A=
Question: Is there a relationship between composition of binary mixture in the liquid phase xA and gaseous phase yA?
Answer: Yes, Raoults law applicable to ideal liquids
pA=pA"xA
CH7
Raoults law
BB p exp( AB ) CB T
,, B
Fact: It does not matter, how much liquid is in the vessel, pressure of vapours is the same, and given by Antoines equation
B HEAVY
Therefore also the molar volume nB/V is independent of amount of liquid.
CH7
Raoults law
p x V nA RT
'' A A
after expansion of nA molecules to volume V
A LIGHT B HEAVY
p AV nA RT
Volume xAV Volume V giving Raoults law
pA pA " xA
xA
CH7
Raoults law
Volume xAV Volume V
A LIGHT B HEAVY
xA
1-xA=xB
,, pB exp( AB
BB ) CB T
CH7
Distillation
Cooling condensing
CH7
H2O+CO2 yCO2
Henrys law
H2O+CO2
xCO2
pCO2 H (T ) xCO2
A LIGHT
CH7
Tutorial
a) Equilibrium temperature T b) Molar composition of vapours
B HEAVY
BB BA ,, ) ) pB exp( AB CB T CA T
yA
xA
CH7
Initial state: Syringe filled by liquid mixture H2O (B) + CH3OH (A) (methylalcohol). Initial volume V0, molar fraction of methylalcohol xA, number of moles nA, nB are given (approximated from density).
V0
V1
VG
VL
CH7
Unknown 9 variables xA=? yA=? p=? VL=? VG=? nAL=? nAG=? nBL=? nBG=? Equations
VG VL V1
'' '' '' p ( pA pB ) x A pB
nA nAL nAG
nB nBL nBG
VL V0 nAL nBL n A nB