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CH7

CHEMISTRY E182019

Phase equilibria G=0 Clausius Clapeyron


This course is approximately at this level
Rudolf itn, stav procesn a zpracovatelsk techniky VUT FS 2010

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T-S diagrams
p=1000 bar
technically realizable maximum

T-s diagrams

Saturated liquid curve

Gas steam
Saturated vapour curve

Liquid

L+G

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T-S diagrams evaporation

T-s diagrams

Saturated liquid s=2 kJ/kgK

Saturated steam s=6 kJ/kgK Enthalpy of evaporation hLG=T(s-s)=5004=2MJ/kg

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Solid-Liquid-Gas
p

Phase diagrams
L-liquid G-gas
p

L-liquid S-solid G-gas

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.

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Solid-Liquid-Gas

Phase diagram ice-water-steam

CRITICAL POINT

Cubic ice Hexagona l ice

TRIPLE POINT

liquid-like hydrogen-bonded clusters dispersed within a gas-like phase

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Solid-Liquid-Gas
Melting hSL>0, sSL>0, GSL=0, dp=dT=0

L-liquid S-solid G-gas

Evaporation hLG>0, sLG>0, GLG=0, dp=dT=0

Sublimation hSG>0, sSG>0, GSG=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.

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Clausius Clapeyron Solid-Liquid-Gas


p

L-liquid S-solid G-gas


Slopes dp/dT are given by Clausius Clapeyron equation

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

Specific volume changes, e.g. vG-vL

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Clausius Clapeyron Solid-Liquid-Gas


p

L-liquid S-solid G-gas


dp/dt>0 because hLG>0 vLG>0 (volume of steam is greater than volume of liquid)

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

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Clausius Clapeyron derivation


dT s dpv
Mechanical workHeat added-difference between
evaporation enthalpy at T+dT and received in one cycle condensation enthalpy at temperature T

Clausius Clapeyron equation can be derived from energy balance of a closed cycle in Ts diagram:

Closed loop (evaporation, expansion, condensation, compression)

dp s h dT v T v

T+dT T

s=s-s

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Clausius Clapeyron and hLG

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)

hLG dp dT T (v '' v ')


State equation

3000

2500

h[kJ/kg]

Antoines equation B ln p A C T

pv ''

RT M

2000

1500

Result can be improved when using Van der Waals


1000

Giving expression for hLG

hLG

RT 2 d ln p RT 2 B M dT M (C T ) 2

500

or Redlich Kwong state equation

0 0 100 200 T [C] 300 400

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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

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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.

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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

and also answer to the previous question

xA

nA xA pA " yA nA nB x A p A " (1 x A ) pB "

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Raoults law
Volume xAV Volume V

A LIGHT B HEAVY

xA

1-xA=xB

p p A pB p A ''(T ) x A pB ''(T )(1 x A )


BA p exp( A A ) CA T
,, A

,, pB exp( AB

BB ) CB T

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Distillation

Initial composition of Liquid Mixture

Cooling condensing

Liquid mixture enriched by heavy component

Liquid mixture enriched by light component

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Liquid noncondensable gas


Given temperature T and molar fraction of dissolved CO2

H2O+CO2 yCO2

'' pCO2 pCO (T ) xCO2 2


What to do if T > Tcrit = 31 oC ?

Henrys law
H2O+CO2
xCO2

pCO2 H (T ) xCO2

Henrys constant can be found in tables

A LIGHT
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Tutorial
a) Equilibrium temperature T b) Molar composition of vapours

B HEAVY

Given total pressure p and molar fraction of liquid phase xA calculate

Nonlinear equation for T (Excel solution)

p p A pB p A ''(T ) x A pB ''(T )(1 x A )


p ,, A exp( A A

BB BA ,, ) ) pB exp( AB CB T CA T

p=const yA Repeated distillation

yA

xA pA " x A p A " (1 x A ) pB "

xA

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Tutorial SYRINGE alcohol


Final state: Volume is increased to V1. Temperature is constant (room temperature).

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).

Calculate pressure p, molar fraction of methylalcohol in liquid and vapour phase.

V0

V1

VG

VL

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Tutorial Syringe alcohol


LINEAR NONLINEAR
'' pA x AVG nAG RT

Unknown 9 variables xA=? yA=? p=? VL=? VG=? nAL=? nAG=? nBL=? nBG=? Equations

VG VL V1
'' '' '' p ( pA pB ) x A pB

'' pB (1 x A )VG nBG RT

nA nAL nAG
nB nBL nBG
VL V0 nAL nBL n A nB

nAL xA nAL nBL

nAG yA nAG nBG

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