Kinetics of Procees Unpredictable-But Reaching Equilibrium Predictable

Thermodynamics THERMODYNAMICS Generalities Purpose: macroscopic description of phenomena involving: Incoherent forms of energy (heat): associated with the
he random microscopic state of individual particles (traslational, rotational, vibrational, electron excitation, etc.) Coherent forms of energy: associated with organized energy forms of macroscopic systems (kinetic, potential, electromagnetic, etc.) Microscopic scales: 23 number of molecules in a mole of substance ! 10 ! 10 "15 s period of vibration of atoms in solids ! 10 separation of atoms in condensed phases Hence: detailed microscopic description is impractical for macroscopic predictions Simple thermodynamic systems: homogeneous isotropic uncharged free of body forces (gravitational, electric, magnetic, etc.) and surface effects
Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.
Thermodynamics GENERAL PRINCIPLES

Subsystem 1
Extensive Parameters Thermodynamic parameters additive over component subsystems:
Y( )
1
Y = !i Y
(i )
Subsystem 2
(2 )
Hence, if Y is a function of other extensive parameters X1 , X2 ,...X M : Y ( ! X1 , ! X2 ,... ! X M ) = !Y ( X1 , X2 ,... X M ) (1st-order homogeneous) Intuitively: extensive parameters are proportional to the system size Examples: volume V , internal energy E , entropy S , composition Ni
!
Subsystem M
Y(
M)
System Thermodynamic Equilibrium Thermodynamic systems react to external or internal changes by modifying their state
Microscopic mobility eventually leads to macroscopically stable equilibrium conditions Thermodynamic equilibrium only depends on system state, not on previous history Hence: at equilibrium the extensive parameters describing the state of simple systems: are linked by a unique functional relation (fundamental thermodynamic relation) are potential functions of the remaining independent parameters (point functions) equilibrium thermodynamics: determines the final equilibrium state reached by the system cannot predict the kinetics of the process leading to equilibrium conditions
Thermodynamics GENERAL PRINCIPLES Internal Energy & the First Law of Thermodynamics For conservative mechanical systems: the energy E is defined as:
dE = dW where dW is the mechanical work done on the system
dQ System dE = dQ + dW dW
For simple thermodynamic systems: it is necessary to generalize the definition of energy to account for heat exchanges: (1st law of thermodynamics) dE = dQ + dW where dQ is the elementary heat transferred to the system E is an extensive thermodynamic parameter called internal energy
Notice: E is a potential function ( dE is a perfect differential) only energy changes, not absolute energy values, are defined neither dQ nor dW are perfect differentials heat and mechanical work are dimensionally consistent and mutually equivalent: 1 cal = 4.1858 J (Joules mechanical equivalent of heat) in moving systems E includes the kinetic energy contribution
Thermodynamics GENERAL PRINCIPLES Walls and Constraints Thermodynamic systems are delimited by walls Through the walls the systems extensive parameters can be controlled and/or constrained With respect to an extensive parameter a wall can be: rigid adiabatic restrictive impermeable nonrestrictive depending on whether it prevents or allows changes of that parameter
System
dN i
diathermal dQ
semidW permeable movable
Common types of physically realizable restrictive/nonrestrictive walls are: adiabatic/diathermal with respect to heat exchanges rigid/movable with respect to volume changes impermeable/permeable with respect to i -th component composition changes
Examples: Heat, volume and composition are constrainable parameters Magnetic dipole moment is an unconstrainable parameter (no restrictive walls exist)
Thermodynamics GENERAL PRINCIPLES Walls and Heat Measurements Any energy state can be reached through an adiabatic introduction of work: (Joules experiment) dE = dW Hence energy changes can be measured in terms of the external work on the system For any energy change dE , the heat transfer is then determined by: dQ = dE ! dW
Closed Systems Simple systems bounded by adiabatic, rigid and impermeable walls
Spontaneous Transformations of Closed Systems Question: how will a closed system evolve after the removal of some internal constraint? Partial Answer: system changes determined by random microscopic adjustments to new conditions the system will spontaneously evolve towards microscopic states of higher probability final macroscopic equilibrium reached for maximum probability of microscopic states Conclusion: spontaneous transformations maximize a new thermodynamic function: the entropy S
Thermodynamics GENERAL PRINCIPLES Entropy & the Second and Third Laws of Thermodynamics Axiomatic entropy properties (generalize observations, confirmed by statistical mechanics): It is a function of the systems extensive parameters, defined for all equilibrium states For simple systems: (fundamental thermodynamic relation) S = S ( E, V , N1 ,... N M ) It is itself an extensive thermodynamic parameter It is a once regular and monotonically increasing function of the internal energy E : " !S % >0 $ ' ! E # & V , N ... N
1 M
The entropy of a closed system at thermodynamic equilibrium is the maximum compatible with the external and internal constraints. for any spontaneous process:
dS ! 0
(2nd law of thermodynamics)
and
!dS = 0 " 2 #d S < 0
at equilibrium
According to Plancks stronger formulation, for any system:

S=0
when the temperature T = ( ! E ! S )V , N ... N = 0 (3rd law of thermodynamics)

1 M
Thermodynamics GENERAL PRINCIPLES Energetic Form of the Fundamental Relation Since ( dS dE )V , N ... N ! 0 : 1 M S = S ( E, V , N1 ,... N M ) !
E = E ( S, V , N1 ... N M ) where:
S = S ( E, V , N1 ,... N M ) ! entropy form of the fundamental thermodynamic relation E = E ( S, V , N1 ... N M ) ! energy form of the fundamental thermodynamic relation
Notice that in the fundamental relations each dependent variable is expressed in terms of a specific set of independent extensive parameters (natural variables)
Specific Properties Extensive properties per unit mole N = m M or mass m , indicated by small letters Let:
N = ! i Ni
xi =
the total number of moles and m = ! i mi
the total mass
Ni m the mole fraction and yi = i the mass fraction of the i -th component N m Then, choosing ! = 1 N (or, alternately, ! = 1 m ), for simple systems:
s = S N = S ( E, V , N1 ,... N M ) N = S ( E N , V N , N1 N ,... N M N ) = s ( e, v, x1 ,... x M )
and, for simple one-component systems ( N = N1 ): s = S N = S ( E, V , N ) N = S ( E N , V N ,1) = s ( e, v )

Thermodynamics GENERAL PRINCIPLES Intensive Parameters Differentiating the energetic fundamental relation E = E ( S, V ,...Ni ...) and defining: " !E % " !E% # "E& = T =$ p = ! , , i % $ # !S ' & V ,... N ... $ "V ( ' S ,... N ... # ! Ni ' & S , V ,... N ...
i i
j (i
obtain:
dE = T dS ! p dV + " i i dNi
(1st law of thermodynamics)
where: T is named temperature

p is named pressure i is named electrochemical potential of the i -th component
are the energetic intensive parameters Need to verify that T , p and i play the usual role of the temperature, pressure and electrochemical potential By comparison with dE = dQ + dW : is the quasi-static (equilibrium) heat input into the system dQ = T dS is the quasi-static mechanical work by the external pressure ! p dV
dWc = ! i i dNi is the quasi-static chemical work due to composition changes
Thermodynamics GENERAL PRINCIPLES Equations of State As derivatives of E ( S, V ,... Ni ...) T , p and i are natural functions of S, V ,... Ni ... : T = T ( S, V ,... Ni ...)
i = i ( S, V ,... Ni ...)
By differentiation w.r.t. the extensive parameter Xi : $ #E ' E (... ! Xi ...) = ! E (... Xi ...) " & = +i (... ! Xi ...) = +i (... Xi ...) % #X ) (
i X j * Xi
p = p ( S, V ,... Ni ...)
(energetic equations of state)
Hence: intensive parameters ! i are 0-th order homogeneous functions of their natural variables Intuitively: intensive parameters are local properties independent on the system size
Problem Show that the intensive parameters and equations of state in the entropic formulation are: 1 1 p p i i and = ( E, V ,... Ni ...) ; = ( E, V ,... Ni ...) = ( E, V ,... Ni ...) T T T T T T
Thermodynamics GENERAL PRINCIPLES Euler Equation Differentiating ! E ( S, V ,... Ni ...) = E ( ! S, !V ,... ! Ni ...) w.r.t. ! and setting ! = 1 obtain the: Euler equation in the energy representation: !E !E !E E ( S, V ,... Ni ...) = S+ V +" Ni ! E = TS " pV + # i Ni !S !V i i ! Ni The Euler equation is: a linear combination of extensive and intensive parameters (or equations of state) equivalent to the fundamental thermodynamic relation Gibbs-Duhem Relation Differentiating the Euler equation:
E = TS ! pV + " i i Ni
with
obtain the Gibbs-Duhem relation in the energy representation: S dT ! V dp + " i Ni di = 0 The Gibbs-Duhem relation: represents a differential equation between the intensive parameters T , p, i Therefore the intensive parameters are once mutually dependent
Thermodynamics PROBLEM Specific Properties Formulation Show that in terms of molar specific properties e = e ( s, v,... xi ...) : the equations of state are: T = T ( s, v,... xi ...)
i = i ( s, v,... xi ...)
the first law writes (hint:
p = p ( s, v,... xi ...)
de = T ds ! p dv + " i i dxi = T ds ! p dv + " i # r ( i ! r ) dxi
!x
i
= 1 ):
the Euler equation writes: e ( s, v,... xi ...) = Ts ! pv + " i i xi the Gibbs-Duhem equation writes:
s dT ! v dp + " i xi di = 0
and for one-component systems ( x1 = 1 ): (energy conservation) de = T ds ! p dv

e ( s, v,... xi ...) = Ts ! pv +
(Euler equation) (Gibbs-Duhem relation)
d = ! s dT + v dp
Thermodynamics THERMODYNAMIC EQUILIBRIUM Entropy Maximum and Energy Minimum Principles From:
dE = T dS ! p dV + " i i dNi # dS = 1 p dE + dV ! " i i dNi T T T
it follows:
( dS )E =
1 1 p dV ! " i i dNi = ! ( dE )S T T
where
T >0
Hence the 2nd law of thermodynamics can be equivalently formulated by the: Maximum Entropy Principle The entropy of any simple closed system at thermodynamic equilibrium is the maximum compatible with the internal constraints and the assigned values of the internal energy and the other independent extensive parameters: d 2S E < 0 ( dS )E = 0 and
( )
or the: Minimum Energy Principle The energy of any simple isentropic system at thermodynamic equilibrium is the minimum compatible with the internal constraints and the assigned values of the entropy and the other independent extensive parameters: d2E S > 0 ( dE )S = 0 and
Thermodynamics THERMODYNAMIC EQUILIBRIUM Intensive Parameters and Thermal Equilibrium Assumptions: closed composite system ( dE = 0 ) two simple subsystems, temperatures T1 and T2 thermal contact through a rigid, impermeable, diathermal wall Internal constraints:
dV1 = dV2 = 0 dNi1 = dNi 2 = 0 for all indexes i
(rigid wall) (impermeable wall)
T1 , dS1 1
T2 , dS2 dQ 2
Thus, using the imposed constraints: dE = dE1 + dE2 = T1 dS1 + T2 dS2 = 0 ! T1 dS1 = "T2 dS2 # 0 Equilibrium condition (maximum entropy principle): dE dE " 1 1 % ( dS )E = ( dS1 )E + ( dS2 )E = 1 + 2 = $ ! ' T1 dS1 = 0 ! T1 = T2 T1 T2 # T1 T2 &
(as expected)
(equality of the intensive parameter corresponding to the exchanged extensive parameter) Confirms the thermodynamic role of temperature as regulating heat exchanges
Problem: Show that the same result is obtained using the minimum energy principle.
Thermodynamics THERMODYNAMIC EQUILIBRIUM Intensive Parameters and Mechanical Equilibrium Assumptions: closed composite system ( dE = 0 ) two simple subsystems, pressures p1 and p2 mechanical contact through a movable, impermeable, adiabatic wall Internal constraints:
dV1 = ! dV2 " 0 dNi1 = dNi 2 = 0 for all indexes i
(movable wall) (impermeable wall)
T1 , dS1 1
T2 , dS2 dV 2
Thus, using the imposed constraints: dE = dE1 + dE2 = ! p1 dV1 ! p2 dV2 = 0
Equilibrium condition (maximum entropy principle): 1 p 1 p ( dS )E = ( dS1 )E + ( dS2 )E = dE1 + 1 dV1 + dE2 + 2 dV2 = 0 ! identically satisfied T1 T1 T2 T2 Hence no equilibrium solution is obtained: in the absence of energy dissipation the system oscillates indefinitely
Problem: Obtain the same result for isentropic systems using the minimum energy principle.
Thermodynamics THERMODYNAMIC EQUILIBRIUM Intensive Parameters and Diffusive Equilibrium Assumptions: closed composite system ( dE = 0 ) two simple subsystems, temperatures T1 and T2 , k -th potentials k1 , k 2 thermal and k -th species diffusive contact thru a rigid, semipermeable, diathermal wall Internal constraints:
dV1 = dV2 = 0 dN k1 = ! dN k 2 " 0 dNi1 = dNi 2 = 0 for all i ! k
(rigid wall) (semipermeable wall) (semipermeable wall)
T1 , dS1 1
T2 , dS2
dQ, dN k
Thus, using the imposed constraints: dE = dE1 + dE2 = T1 dS1 + T2 dS2 + k1 dN k1 + k 2 dN k 2 = 0 Equilibrium condition (maximum entropy principle): 1 1 ( dS )E = ( dS1 )E + ( dS2 )E = dE1 + dE2 ! k1 dNk1 ! k 2 dNk 2 = T1 T2 T1 T2
"T1 = T2 ! # $ k1 = k 2 (equality of the intensive parameters corresponding to the exchanged extensive parameters)
"1 1% " % = $ ! ' dE1 ! $ k1 ! k 2 ' dN k1 = 0 T2 & # T1 T2 & # T1
Confirms the thermodynamic roles of T and k as regulating heat and mass exchanges.
Thermodynamics ALTERNATIVE FORMULATIONS Motivations Intensive parameters usually more easily controlled (for instance p and T w.r.t. V and S ) Express equilibrium conditions in terms of intensive, rather than extensive, parameters
Objective Given a equation of the extensive variables X1 ,...X M : Y = Y ( X1 ,...X M ) find a mathematically equivalent function: ! = ! ("1 ,..."M ) of the intensive variables: !1 = " Y " X1 , ... !M = " Y " X M i.e.: classical Legendre transformation problem In one dimension, for any X and Y ( X ) , the envelope of the intercepts: ! (" ) = Y # " X as functions of the slope ! = dY dX uniquely determines the curve Y ( X ) and viceversa Also, from the definitions of ! and ! : ( ! is the independent variable, as expected) d! = dY " X d # " # dX = " X d #
Y = Y(X)
( X, Y )
tan "
X
!1
Thermodynamics ALTERNATIVE FORMULATIONS Legendre Transforms In the multidimensional case, the Legendre transform of Y ( X1 ,... X M ) w.r.t. X1 ,... Xr is:
! ("1 ... "r , Xr +1 ... X M ) = Y [ X1 ,... Xr ] = Y # $ "i Xi

i =1
d! = " $ Xi d #i +
i =1
i = r +1
$ # dX
i
Thermodynamic Potentials Legendre transforms of the internal energy: Helmholtz potential or free energy: F = E [ S ] = E ! TS where enthalpy: H = E [ V ] = E + pV
F = F ( T , V , N1 ,... N M )
dF = ! S dT ! p dV + 1 dN1 + ... + M dN M
where
H = H ( S, p, N1 ,... N M )
dH = T dS + V dp + 1 dN1 + ... + M dN M
Gibbs potential or free enthalpy: G = E [ S, V ] = E ! TS + pV where
G = G ( T , p, N1 ,... N M )
dG = ! S dT + V dp + 1 dN1 + ... + M dN M
Thermodynamics ALTERNATIVE FORMULATIONS Minimum Principle for Thermodynamic Potentials Applies to systems at equilibrium with one or more intensive parameters ! j kept constant System exchanges the extensive parameter X j with the reservoir to stabilize ! j = ! (j r ) Constraints:
dX j = ! dX (j r )
dXi = dXi( r ) = 0
! d 2 X j = " d 2 X (j r )
for all indexes i ! j
System
Reservoir dX (j r)
!j
dX j
!j
At equilibrium for the combined system and reservoir:
d E + E ( r ) = dE + ! (j r ) dX (j r ) = dE " ! j dX j = d E " ! j X j
d 2 E + E ( r ) = d 2 E + ! (j r )d 2 X (j r ) = d 2 E " ! j d 2 X j = d 2 E # $Xj % &

Thus, for systems at thermodynamic equilibrium: ! j " constant # E $ %Xj & ' " minimum
!j
!j
= d E# $Xj % &
!j
=0
!j
>0
In particular, the equilibrium conditions for simple systems are: E ! minimum at constant entropy S and volume V F ! minimum at constant temperature T and volume V
H ! minimum
G ! minimum
at constant entropy S and pressure p at constant temperature T and pressure p
Thermodynamics THERMODYNAMIC DERIVATIVES Maxwell Relations Integrability conditions of thermodynamic potentials Recall, for simple multicomponent systems:
dF = ! S dT ! p dV + " i i dNi dG = ! S dT + V dp + " i i dNi

Thus, for example: " !2E % " !2E % = $ # ! S !V ' & ... N ... $ # !V!S ' & ... N
k
dH = T dS + V dp + ! i i dNi
...
" !p% " !T % ( )$ = # !S ' & ... Nk ... $ # !V ' & ... Nk ...
For simple single component systems: 7 thermodynamic potentials, E , E [ S ] , E [ V ] , E [ N ] , E [ S, V ] , E [ S, N ] and E [ V , N ] 6 variables (3 extensive + 3 intensive) per each thermodynamic potential 7 ! 3 = 21 independent Maxwell relations
Thermodynamics THERMODYNAMIC DERIVATIVES Thermodynamic Derivatives for One-Component Systems In one-component systems only 3 derivatives are independent, usually chosen as: 1 # "V & 1 # "v & !p = % = the coefficient of thermal expansion: V $ "T ( 'p v% $ "T ( 'p the isothermal compressibility: the molar heat capacity at constant pressure:
!T = "
cp =
1 $ #V ' 1 $ #v ' = " V& v& % # p) (T % # p) (T
" !s % " !q % T " !S % = T = $ N$ # !T ' &p # !T ' &p $ # !T ' &p
which are normally tabulated as functions of T and p To express the thermodynamic derivatives of simple substances in terms of ! p , !T and c p : 1) 2) 3) 4) eliminate the derivatives of eliminate the derivatives of eliminate the derivatives of eliminate the derivatives of E , H , F and G using their differential definitions using of the Gibbs-Duhem relation S using Maxwell equations or the definitions of c p and cv V using the definitions of ! p and !T
Thermodynamics THERMODYNAMIC DERIVATIVES Useful Differential Expressions If z ( x, y ) is constant:

" !z % " !z % dz = $ ' dx + $ ' dy = 0 # !x& y # !y& x
and therefore: " !x% " !z % = ( $ $ # !y' &x # !y' &z
" !z % " !y% = 1 $ $ # !x' &y # !x' &z
Besides, if ! ( x ( w ) , y ( w ) , z ( w )) and z are both constant, differentiating w.r.t. w :
# !" & # ! x & # !" & # ! x & + % % ( =0 $ !x ( ' y, z % $ !w ( 'z % $ !y ( ' x,z $ ! w ' z # "! & # "! & d! = % dx + dy = 0 % $ "x ( ' y, z $ "y ( ' x,z
$ "# ' ! & % "y ) ( x,z

$ "# ' ! & % "y ) ( x,z
$ "# ' $ "x ' = * & & % "x ) ( y, z % "w ) (z

$ "x' $ "# ' = * & & % "x ) ( y, z % "y) (z
$ "y ' & % "w ) (z
but also:
Thus, eliminating ! from these equations:

" !x% " !x % = $ ' $ # !y' & z # !w & z " !y % $ # !w ' &z
Thermodynamics THERMODYNAMIC DERIVATIVES Specific Heats Considering T dS as a function of T and p and recalling dG = ! S dT + V dp : " !S % " !S % " !V % T dS = T $ ' dT + T $ ' dp = Nc p dT ( T $ dp = Nc p dT ( TV) p dp = # !T & p # !T ' &p # ! p&T
*" ! p % " !p% = Nc p dT ( TV) p ,$ ' dT + $ dV / ' # !V & T +# ! T & V .

Thus:
TV) p " ! p % TV) p ( ! V ! T ) p )2 T " !S % p cv = $ ' = c p ( = cp + = c p ( Tv $ ' N # !T & V N # !T & V N ( ! V ! p )T *T
Isentropic Compressions and Expansions With the above procedure:

1 $ #V ' 1 $ #S ' = % # p) (V % #p) (S V & V& 1 *$ # S ' $ #S ' = & & ) % #V ) (p V , +% # T ( V $ # p' & % #T ) (V / .
2
!S = "
*$ # S ' ,& ) % (p # T +
$ #V ' & % #T ) (p/ .
c $ #T ' = v & ) Vc p % # p ( V
0p cv $ # V ' cv $ #T ' = " = ! = ! " Tv & T T % #V ) (p % #p) ( T cp Vc p & cp
Thermodynamics THERMODYNAMIC DERIVATIVES Free Expansions No work nor heat exchanges:
! E = !Q + !W = 0
Hence: " !T % " !E% = ( $ $ # !V ' &T # !V ' &E
= 1 Ncv ) " !S % , 1 ) " ! p% , " !E% " !S % = ( T ( p T = p ( T $ ' $ ' $ ' + .= + $ . # !T ' &V # & # & # & ! V ! T Nc ! T * T V Vv * " !V % , p T /p = ( . $ # !p' & T - Ncv Ncv 0T
) " !V % +p + T$ ' # &p ! T *
Throttling Expansions Adiabatic volume and pressure changes, and: ! E = ! W = p1V1 " p2V2 = " ! ( pV ) # ! H = !( E + pV ) = 0 Hence:
" !T % " !H% = ( $ $ # !p ' &T # ! p' &H = v / pT ( 1 cp
) " !S % , V " !H% " !S % = v + T T = ( . $ $ ' $ ' # !T ' &p + # &p # & ! p ! T nc p * T-
) T " !V % , +1 ( $ .= ' # & V ! T + p. * -
i.e. the temperature change switches sign at the inversion temperature Ti = 1 ! p (if any)
Thermodynamics IDEAL GASES Generalities Composed by non-interacting atoms or molecules (except for conservative collisions) Limit behavior of real gases at low pressure and density, i.e. far from their critical point Experience and theoretical considerations show that for ideal gases: (thermodynamic, or mechanical, equation of state) pV = NRT where R = 8.3144 J/mole K is the universal gas constant E = Ne ( T ) (caloric equation of state) i.e. the molar internal energy is function of the temperature only F ( T , V ,... Ni ...) = ! i Fi ( T , V , Ni ) (Gibbs theorem) i.e. the free energy of multicomponent ideal gases is additive over the component species Ideal gases are classified as: general when cv = cv ( T ) (function of the temperature only) simple when cv is constant Simple ideal gases, from equipartition of energy: e= 1 where N f is the number of active degrees of freedom 2 N f RT
F ( V , T, N1 + N2 )
=
F ( V , T , N1 )
+
F ( V , T, N 2 )
Thermodynamics IDEAL GASES The Thermodynamic Equation of State For a perfect gas : NRT where ! R ! 8"31 J mole K is the universal gas constant p= V Alternative forms: using the definitions of the molecular weight ! M ! m N and the density !! ! m V : NRT mRT p= = = ! RT V MV where R = R M is the gas constant using the no. of particles N p and the definition of the Avogadros no. N A = N p N : NRT N pRT N p kBT p= = = V N AV V where !kB = R N A ! 1.38 ! 10 "23 J molecule K is Boltzmann constant By definition: m N pmp N p N= = = M M NA
M mp
! NA =
where m p is the particle mass

Thermodynamics IDEAL GASES One-Component Ideal Gas From: T "de = T ds ! p dv de ' &s * ' &e * % c = T = = % e = e + cv ( T - ) dT # ) , ) , v o . To ( + ( + e = e T & T & T dT ( ) v v $ T c (T " ) c (T ) 1 p dv v ds = de + dv = v dT + R ! s = so + # v dT " + R ln To T T T v T" vo Hence the internal energy and the entropy are: E = Ne = N eo + ! cv ( T " ) dT "
To
T c (T ! ) # V No & S = Ns = N % so + " v dT ! + R ln To T! Vo N ( $ '
From the relevant definitions: the Helmholtz potential:

T T c (T " ) $ V No ' F = Nf = N ( e ! Ts ) = N & eo + # cv ( T " ) dT " ! Tso ! T # v dT " ! RT ln To To T" Vo N ) % (
electrochemical potential: 1 " !F% eo 1 = $ = ( s + R + o T T #!N' T & T ,V T
To
cv ( T ) ) dT ) ( *
cv ( T ) ) V No dT ) ( R ln To T) Vo N
T
Thermodynamics IDEAL GASES Multi-Component Ideal Gas Helmholtz potential:

T T c (T " ) % V No ( F = ! Ni fi ( T , V , Ni ) = ! Ni ' eoi + # cvi ( T " ) dT " $ Tsoi $ T # vi dT " $ RT ln To To T" Vo Ni * & ) i i
Entropy:
T c (T ) ) # V No & # "F& vi S = !% = N s + d T + R ln = + Ni si ) + i % oi * ( To $ "T ( ' V ,... Ni ... T V N ) $ ' i i o i
Internal energy:
i
E = F + TS = # Ni eoi + " cvi ( T ! ) dT ! = # Ni ei

To i
Pressure:
# "F& RT RT p = !% = N = N ) iV V $ "V ( ' T ,... Ni ... i

(Daltons law of partial pressures)
p = ) pi
i
where
pi = xi p = Ni
RT V
Electrochemical potential: i 1 " ! F % eoi 1 = $ = ) s + R + oi T T # ! Ni ' T & T , V ,... N j (i ... T
To
cvi ( T * ) dT * ) +
cvi ( T * ) V No dT * ) R ln To T* Vo Ni
T
Thermodynamics IDEAL GASES Multi-Component Ideal Gas (continued) Molar specific heat at constant volume: T " !S % 1 cv = $ = ( Nicvi = ( xicvi N # !T ' & V ,... N ... N i i
i
Thermal expansion and isothermal compressibility (from pV = NRT ):
!p =
1 # "V & 1 = % ( V $ " T ' p ,... Ni ... T
and
!T = "
1 $ #V ' 1 = % #p) ( T ,... Ni ... p V&

S ( E1 + E2 , V1 + V2 , N1 + N2 )
Molar specific heat at constant pressure (Meyers relation): TV! 2 Vp p c p = cv + = cv + = cv + R N"T NT Hence: T " !S % 1 cp = $ = ( Nic pi = ( xic pi N # !T ' & p ,... N ... N i i
i
>
S ( E1 , V1 , N1 ) + S ( E 2 , V2 , N 2 )
Notice: ideal gas model does not satisfy Nernsts theorem and cannot be valid as T ! 0 entropy difference with individual components at the same T and p ( Vi = V Ni N ): N& # !S = " ) % NiR ln i ( (entropy of mixing) $ ' N i
Thermodynamics REAL GAS MODELS Ideal van der Waals Fluids Modified mechanical equation of state for real gases (J. D. van der Waals, 1873): RT a pv v a p= ! 2 " Z= = ! (compressibility factor) v!b v RT v ! b RTv where a and b are constants characteristic of the specific gas and accounting for: intermolecular attractive forces, a v 2 , scaling with the no. of molecules pairs the intrinsic volume of the molecules, b Phase Separation & Critical Point Phase separation first occurs at the critical point when two solutions for v become possible at T and p fixed For this to happen: and dp dv = 0 d 2 p dv 2 = 0
p pcr Tcr
from which the critical properties are: 8a a vcr v vcr = 3b , Tcr = and pcr = 2 27 bR 27 b In the reduced variables pr = p pcr , Tr = T Tcr , vr = v vcr the van der Waals equation is: 8Tr 3 1 9 and pr = ! 2 Z = Z ( Tr , vr ) = ! 3vr ! 1 vr 1 ! 1 3vr 8Tr vr
Thermodynamics REAL GAS MODELS Thermal Equation of State of Ideal van der Waals Fluids Need a thermal equation of state 1 T = f ( e, v ) satisfying the integrability condition for ds : 1 p p R a where by hypothesis (van der Waals eqn) ds = de + dv = ! 2 T T T v!b v T and therefore: ! " 1% ! " p% a ! " 1% ! " 1% ! " 1% = =( 2 ) 1 * $ ' + ( (1) * =0 $ ' $ ' $ ' $ ' # & # & # & # & # & !v T e !e T v v !e T v !e T a v ! (a v) T e By introducing the invertible transformation: # $ &! e !" = 1 % e = e (! , " ) with % $ a v = a v ! , " ( ) ( ) & % '! ( a v ) !" = #1 & the above PDE for 1 T transforms in the ODE:
and
J=
! ( e, a v ) $0 ! (" , # )
f (! ) " C1
! " 1 % !e ! " 1 % ! (a v) d " 1 % 1 + = = 0 ) = f (* ) with $ ' $ ' $ ' ! e # T & a v !( ! ( a v ) # T & e !( d( # T & T
Integrating the conditions for e and a v , the simplest invertible transformation is:
1 $ $e = ! + " 1 (! = 2 ( e # a v ) ' ' = f (e + a v) % % 1 a v = # ! + " T & ( &" = 2 ( e + a v ) By analogy with simple ideal gases (where 1 T = cv e ) assume:
1 T = cv ( e + a v ) ! e = cv T " a v ! h = e + pv = cv T + RT v ( v " b ) " 2 a v
Thermodynamics REAL GAS MODELS Fundamental Equation of Ideal van der Waals Fluids Obtain the entropic fundamental equation of an ideal van der Waals fluid by integration of: 1 p ds = de + dv T T where by hypothesis: RT a and p= ! 2 v!b v Hence:
ds = " R cv a cv de + $ ! 2 e+a v #v!b v e+a % dv v' &
1 cv = T e+a v
Integrating along coordinate directions from initial conditions so = s ( eo , vo ) and s = s ( e, v ) : s = so + cv ln and: e + a vo v!b e+a v e+a v v!b + R ln + cv ln = so + cv ln + R ln eo + a v o vo ! b e + a vo eo + a v o vo ! b
S = Nso + Ncv ln
E N + aN V V N!b + NR ln Eo N o + aN o Vo Vo N o ! b
Thermodynamics REAL GAS MODELS The Virial Expansion Real gases approach ideal gases at low densities and deviate appreciably at high densities Expand the fundamental equation in powers of 1 v about the ideal gas behavior Using T and v as independent variables: ! B (T ) f = fideal + RT " k k k = 1 kv Obtain:
where Bi ( T ) is the i -th coefficient of the so-called virial expansion RT ) Bk ( T ) #"f & p = ! % ( = pideal + * $ "v ' T v k =1 v k
2 ( 1 d ( Bk T ) " !s % cv = T $ ' = cvideal + RT ) k # !T & v dT 2 k = 1 kv
) TBk ( T ) 1 d+ #"f & , . s = ! % ( = sideal + R * k $ "T ' v dT k = 1 kv
e = f + Ts = eideal + RT -
1 k k = 1 kv
% ) d! ' "TBk ( T ) # $' B T + ( ) & k * dT ' ' ( +
Thermodynamics REAL GAS MODELS The Law of Corresponding States Deviations from perfect gas behavior increase near critical conditions and: are qualitatively similar for most fluids with nonpolar molecules are effectively correlated in terms of the reduced variables p pcr , v vcr and T Tcr Hence for normal fluids the compressibility factor Z = pv RT : essentially satisfies the same equation of state in the reduced variables p pcr , T Tcr is affected by dissociation at high temperatures for polyatomic gases
air
Thermodynamics REAL GAS MODELS Real Gas Mixtures Kays rule approximation (empirical) The mixture is assimilated to a single real gas with pseudocritical properties defined as: pcr = ! pcr , i (pseudocritical pressure)
Tcr = ! Tcr , i
i
(pseudocritical temperature)
where pcr , i and Tcr , i are the critical pressures and temperatures of the i -th component Pseudocritical properties can then be used (as for a single-component real gas) for: obtaining the reduced properties (pressure p pcr and temperature T Tcr ) of the mixture p T and pr = Tr = pcr Tcr and estimating its behavior from standard plots of the compressibility factor or to: compute the parameters of a two-parameter real gas model For instance, for van der Waals fluids: 2 RT 27R 2Tcr and b = cr a= 8 pcr 64 pcr from which the thermodynamic behavior of the real gas mixture can be evaluated
Thermodynamics THERMODYNAMIC PROCESSES Thermodynamic Transformations Reversible ( dS = 0 ), visualized as a sequence of equilibrium states Irreversible ( dS > 0 ), cannot be described by equilibrium thermodynamics Real (spontaneous) processes: inherently irreversible closely approach reversible processes if slow w.r.t. their typical relaxation time ! Examples: pressure adjustments, relatively fast: ! " L a (sound speed) heat transfers, relatively slow: ! " L2 # (thermal diffusion velocity) where: L is the macroscopic length scale is the sound speed is the thermal diffusivity
a !
Thermodynamics THERMAL MACHINES Performance Limitations and Parameters For a continuous or cyclic machine (subscript M ): and dEM = dQ1 ! dQ2 ! dW = 0 dSM = 0 For the composite (closed) system: dQ dQ dS = ! 1 + 2 + dSM " 0 T1 T2 Eliminating dQ2 :
# T & dW ! % 1 " 2 ( dQ1 = dWr T' $
1
Heat Source T1 dQ1 Work Source dW Thermal Machine dQ2 Heat Sink T2
(reversible work)
Thermal engines: convert heat from hot sources into work ( T1 > T2 , dQ1 > 0 , dWr > 0 ) dWr T (engine efficiency) !e = = 1" 2 dQ1 T1 Refrigerators: use work to subtract heat from cold sources ( T1 < T2 , dQ1 > 0 , dWr < 0 ) dQ1 T1 (refrigerator efficiency) !r = = ( " dWr ) T2 " T1 Heat pumps: use work to add heat to hot sources ( T1 > T2 , dQ1 < 0 , dWr < 0 )
!p =
( " dQ1 ) = T1 ( " dWr ) T1 " T2
(heat pump efficiency)
Thermodynamics TEMPERATURE SCALES Temperature and Entropy Measurements Operational definition of temperature: T2 dWr in terms of the optimum performance of thermal machines = 1! T1 dQ1 Determines temperature ratios from the zero value corresponding to: dWr = dQ1 Absolute temperature scales defined by assigning the temperature of a reference state Triple point of water is commonly used and conventionally corresponds to: 273.16 K in the Kelvin (SI) temperature scale 491.688 R ( 9 5 of the Kelvin value) in the Rankine temperature scale For practical reasons, shifted scales are also used: Celsius temperature scale: ! C = ! K ! 273.15 9 Fahrenheit temperature scale: ! F = ! C + 32 5 where the freezing and boiling points of water at standard atmospheric pressure temperature correspond to values close to 0 and 100 C (32 and 212 ! F , respectively)
Thermodynamics THERMODYNAMIC CYCLES Carnot Cycle (C and D inverted in the diagram?) Assumptions: an isothermal heat addition (AB) an isentropic expansion (BD) an isothermal heat rejection (DC) an isentropic compression (CA) to the original state From energy conservation for the entire cycle: ! E = QAB + QDC + WBD + WCA = 0 On isothermal transformations: # %QAB = T1 ( S1 " S2 ) ! $ Q = T !S % &QDC = T2 ( S2 " S1 ) If the c ycle is used in a thermal engine: ! W = ! ( WBD + WCA ) = QAB + QDC = ( T1 ! T2 ) ( S1 ! S2 )
Q = QAB = T1 ( S1 ! S2 )
T1 T2
S2
S1 S
is the useful work is the absorbed heat
Therefore the engine efficiency of the cycle is: W T !=" = 1" 2 QAB T1
Thermodynamics THERMODYNAMIC CYCLES Otto Cycle Assumptions: a constant volume heat addition (AB) an isentropic expansion (BC) a constant volume heat rejection (CD) an isentropic compression (DA) to the original state perfect gas From energy conservation for the entire cycle: ! E = QAB + QCD + W = 0 If the fluid is a perfect gas: Q = cv !T on isochors (constant volume transformations) TV ! "1 = const Hence:
QAB = cv ( TB ! TA ) , QCD = cv ( TD ! TC )
V2 V1
A
S1
S2 S
on isentropics
and
) "1
TD TC ! V1 $ = = TA TB # " V2 & %
' (1
Therefore the engine efficiency of the cycle is:
( " W ) = 1 + QCD !=
QAB QAB
#V & T "T = 1+ D C = 1" % 1 ( TB " TA $ V2 '
Thermodynamics THERMODYNAMIC CYCLES Brayton (or Joule) Cycle Assumptions: a constant pressure heat addition (AB) an isentropic expansion (BD) a constant pressure heat rejection (DC) an isentropic compression (CA) to the original state perfect gas
From energy conservation for the entire cycle: ! E = QAB + QCD + W = 0 If the fluid is a perfect gas: Q = c p !T on isobares (constant pressure transformations)
p(! "1) / ! T = const
on isentropics
QCD = c p ( TD ! TC )
Hence:
QAB = c p ( TB ! TA ) ,
and
TD TC ! p2 $ = = TA TB # " p1 & %
() "1)
)
(' (1)
'
W Q T " TC T " TB # p2 & !=" = 1 + CD = 1 + D = 1+ A QAB QAB TB " TA TB " TA % $ p1 ( '
#p & = 1" % 2 ( $ p1 '
() "1)
Thermodynamics THERMODYNAMIC CYCLES Diesel Cycle Assumptions: a constant pressure heat addition (AB) an isentropic expansion (BC) a constant volume heat rejection (CD) an isentropic compression (DA) to the original state perfect gas From energy conservation for the entire cycle: ! E = QAB + QCD + W = 0 If the fluid is a perfect gas: Q = cv !T on isochors TV ! "1 = const Hence: on isentropics
QCD = c p ( TD ! TC ) ,
p
A B C D
p1
p3 p2
V2
V1 V
Q = c p !T
p(! "1) / ! T = const
on isobares on isentropics
! "1
QAB = c p ( TB ! TA ) ,
TA TD = ( V1 V2 )
# "1 #
TC TB = ( p3 p1 )
(! "1)
!="
c (T " T ) W Q 1 TB ( p2 p1 ) " TD = 1 + CD = 1 + v D C = 1 " QAB QAB c p ( TB " TA ) # TB " TD ( V1 V2 )# "1
Thermodynamics PROBLEM Pressure-Fed Liquid Propellant Feed System In rockets with gas pressurized fuel feed systems the propellant is transferred from the storage tank (subscript T ) to the combustion chamber under the action of a gas contained in a pressurized bottle (subscript b ), as shown in the figure. Let the pressure pT in the tank be kept constant by a pressure regulator, and assume that the transformation of the perfect gas in the bottle is adiabatic, with constant specific heats and ! = c p cv . Show that the minimum volume of the bottle for rocket operation in vacuum is: pT Vb = ! VT pbi " pbf What pressurizing gas would be more suitable from the thermodynamic point of view? How would the situation change for rocket operation in the atmosphere? Clearly, better performance would be obtained from isothermal or even isobaric transformation of the pressurizing gas by injecting heat in the ! to the combustion bottle. Assuming constant propellant consumption m chamber, what instantaneous and overall heat inputs would be the necessary in the two cases?
pb , Vb
pT , V T
Thermodynamics PROBLEM Supercritical Liquid Propellant Feed System In rockets with supercritical fuel storage systems the propellant is contained in supercritical conditions in a storage tank in order to avoid the problems associated with the presence of two phases (sloshing, bubbles, cavitation, feed continuity, etc.), and is transferred to the combustion chamber by a compressor or a pump, as shown in the figure. In order to obtain a supercritical transformation at constant pressure it is necessary to supply heat to the storage tank when fuel is extracted. Show that, with standard notations, the instantaneous pressure change is expressed by: " !h % dp " ! p % 1 * ! !($ ' / =$ ' ,Q ) m dt # ! e & ( m , # !( & p / + . ! is the heat input rate, and where m is the mass of propellant in the tank, Q ! the rate of propellant consumption. What is the expression for the m temperature change? Compute the heat input per unit propellant mass in steady state conditions as a function of the tank pressure above the critical point for an ideal van der Walls fluid.
Q
p, !
Formulate in the appropriate independent variables the differential problem for the pressure time history in the tank in the two limit operational conditions: a) no propellant consumption ! = hT ( T ! Ta ) , with constant heat exchange coefficient h and a heat leakage expressed by Q T ! with negligible heat and ambient temperature Ta ; b) constant propellant consumption m input.
Thermodynamics THERMODYNAMIC STABILITY Local Stability Consider a system with fundamental equation: S = S( X ) splits in two portions with: X A and X B = X ! X A its entropy varies from: S ( X ) to S! ( X ) =
S ( XA ) + S ( XB ) 2
For infinitesimal fluctuations dX : " X A = X ! dX # $ X B = X + dX and:
S ( X " dX ) + S ( X + dX ) 1 d 2S 2 S! ( X ) = ! S( X ) + dX ( ) 2 4 dX 2 Hence the thermodynamic equilibrium condition: d 2S !0 requires S! ( X ) " S ( X ) dX 2 and is violated between the inflection points A and B
Thermodynamics THERMODYNAMIC STABILITY Global Stability and Phase Separation For finite fluctuations ! X : # XA = X ! "X $ % XB = X + " X and a system with X P ! X ! XQ can acquire an entropy:
XQ XP S! = S ( XP ) + S XQ X P + XQ X P + XQ
( )
the stability condition: S ( X 2 + ! X ) + S ( X 2 " ! X ) # 2S ( X 2 ) is violated also beyond the inflection points A and B (less restrictive than local stability) Hence the system will spontaneously partition in two subsystems with different entropies: a subsystem X P = X 2 ! " X with entropy SP a subsystem XQ = X 2 + ! X with entropy SQ and the maximum allowable value of ! X This phenomenon is essentially responsible for phase transitions
Thermodynamics THERMODYNAMIC STABILITY Local Stability Relative extremes of a multivariable function ! = ! ( x1 , x M ) are the solutions of: if " is minimum $ & Hr ! 0 ! xi = 0 for i = 1,... M with for r = 1,... M % r & '( #1) Hr ! 0 if " is maximum $ where Hr is the determinant of the r -th minor of the matrix " #! xi x j % Local stability conditions for a simple substance: 2 see ! 0 or svv ! 0 and see svv ! sev " 0 in the entropy representation s ( e, v ) 2 ess ! 0 or evv ! 0 and ess evv ! esv " 0 in the energy representation e ( s, v ) For E [ Xi ] = U ! Xi"i and E ! " Xi , X j # $ = E % Xi&i % X j& j , if k ! i, j : ' Xi # Xi '!i $ and E!i !i [ Xi ] = E!i !i " X , X = & = & 1 = & 1 E E X = " =0 [ ] i j X X i X ! # % i i k i ' Xi '!i # Xk '! j ' Xi $ E Xk Xk [ Xi ] = E Xk Xk ! Xi , X j # E! j !i " X , X = & = & 1 = & 1 EXi X j and " $ = E Xk Xk # i j% ' Xi '! j Thus, for h ( s, p ) , f ( T , v ) , and g ( T , p ) the local stability conditions imply:
hss = ess ! 0 fTT = ! 1 ess " 0 gTT = ! 1 ess " 0
or h pp = ! 1 evv " 0 or fvv = evv ! 0 or g pp = ! 1 evv " 0
and and and
! hss h pp " 0
a saddle for h ( s, p ) a max for g ( T , p )
! fvv fTT " 0

2 gTT g pp ! gTp "0
a saddle for f ( T , v )
Thermodynamics THERMODYNAMIC STABILITY Local Stability & Thermodynamic Derivatives Local stability constraints the behavior of thermodynamic derivatives of simple systems For instance: 1 # "T & 1 see = ! 2 % ( = ! 2 ) 0 * cv + 0 T $ "e ' v T cv
1 # " p& fvv = ! % ( = * 0 + )T * 0 $ " v ' T v)T

where: cv = T ( ! s ! T ) v !T = " ( # p # v )T v Besides, since: Tv" 2 p c p ! cv = #T c p ! cv ! 0 is the specific heat at constant volume is the isothermal compressibility
and
where ! S = ( " p " v )s v is the isentropic compressibility, it follows that:
! S cv = !T c p
!T " ! S " 0
Thermodynamics THERMODYNAMIC STABILITY Phase Transitions Equilibrium condition at T , p ! constant : min g T , p

g
p ! constant T" Ttr T ""
{ }
For the case in the figure, at the temperature T ! ( T !! ): A! ( B!! ) is the equilibrium point (absolute min)
B! ( A!! ) is the metastable equilibrium point (relative min)
gtr
A' A A" vA
B' B B" vB
At the transition temperature Ttr , both A and B : are equivalent equilibrium points correspond to different phases of the system Approaching the critical point on the saturation curve: p = psat ( T ) A and B tend to coalesce
g
p = psat
Tcr , pcr
gas liquid
gcr
Tcr
solid
p
A vA
vcr v B v
Thermodynamics THERMODYNAMIC STABILITY Lever Rule in Phase Mixtures If A and B indicate the two phases in a mixture: and therefore E = N A e A + N B eB = ( N A + N B ) e and so on for all extensive properties Phase Coexistence Curves and Latent Heats On the coexistence curve between the phases A and B: the latent heat of the transition from phase A to phase B is: q AB = T ( sB ! s A ) = hB ! hA
e = x A e A + x B eB
(lever rule)
Tcr , pcr
gas liquid
solid the equilibrium condition is: p A = B ! d A = d B Using d = ! s dT + v dp , the Clapeyron equation is obtained: dp sB ! s A q AB ! ( sB ! s A ) dT + ( v B ! v A ) dp = 0 and therefore = = dT v B ! v A T ( v B ! v A )
On the vaporization line, for vV ! RT p >> v L (Clausius-Clapeyron equation):
( qvap " 1 1 % + p = exp * ! ! '$ po ) R # T To & , if qvap , almost independent on p and slowly varying with T , is taken to be constant
dp qvap pqvap ! ! dT TvV RT 2 which integrates to
Thermodynamics THERMODYNAMIC STABILITY Unstable Isotherms The positive slope portion CE of subcritical van der Waal isotherms: does not satisfy the local stability condition: " ! p% (0 $ # !v ' &T does not represent a physically realizable process Phase transition occurs between some points B and F The branches BC and EF are locally stable, but globally unstable Interphase equilibrium at points B and F requires pB = pF and B = F Being d = ! s dT + v dp , on the given isotherm:
p
A B D C E F G
B ! F =
"
pF pB
v dp = 0
(the two shaded areas in the figure are equal)
The physically observed globally stable isotherm between point B and F is the straight segment BF which satisfies the above condition with pB = pF
Thermodynamics THERMODYNAMIC STABILITY Thermodynamic Degrees of Freedom of Multicomponent Systems For instance, in the energy representation: or in molar form E = E ( S, V , N1 N M )
e = e ( s, v, x1 x M !1 )
local and global stability correspond to relative and absolute minima of E or e In a system with: P phases (indexes j and k ) M components (index i ) the equilibrium conditions for the transfer of the i -th component between all phases are:
( j) ( j) (k ) (k ) (k ) i( j ) T , p, x1 ,... x M T , p, x1 ,... x M !1 = i !1
for i = 1,... M and j ! k
which represent: M ( P ! 1) equations ( j) ( j) in 2 + ( M ! 1) P independent variables T , p and x1 ,... x M ! 1 for each phase j = 1, P Hence the number of independent parameters (thermodynamic degrees of freedom) is: (Gibbs phase rule) N dof = M ! P + 2 For single component systems ( M = 1 and P = 1 ): N dof = 2 for single phase points N dof = 1 on the coexistence curves between two phases N dof = 0 for triple points where three different phases are in mutual equilibrium

Kinetics of Procees Unpredictable-But Reaching Equilibrium Predictable

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Thermodynamics THERMODYNAMICS Generalities Purpose: macroscopic description of phenomena involving: Incoherent forms of energy (heat): associated with the

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

Thermodynamics GENERAL PRINCIPLES

Extensive Parameters Thermodynamic parameters additive over component subsystems:

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

semidW permeable movable

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

(2nd law of thermodynamics)

!dS = 0 " 2 #d S < 0

According to Plancks stronger formulation, for any system:

when the temperature T = ( ! E ! S )V , N ... N = 0 (3rd law of thermodynamics)

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

the total number of moles and m = ! i mi

the total mass

and, for simple one-component systems ( N = N1 ): s = S N = S ( E, V , N ) N = S ( E N , V N ,1) = s ( e, v )

(1st law of thermodynamics)

where: T is named temperature

dWc = ! i i dNi is the quasi-static chemical work due to composition changes

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

(energetic equations of state)

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

de = T ds ! p dv + " i i dxi = T ds ! p dv + " i # r ( i ! r ) dxi

and for one-component systems ( x1 = 1 ): (energy conservation) de = T ds ! p dv

(Euler equation) (Gibbs-Duhem relation)

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

dV1 = dV2 = 0 dNi1 = dNi 2 = 0 for all indexes i

(rigid wall) (impermeable wall)

dV1 = ! dV2 " 0 dNi1 = dNi 2 = 0 for all indexes i

(movable wall) (impermeable wall)

Thus, using the imposed constraints: dE = dE1 + dE2 = ! p1 dV1 ! p2 dV2 = 0

dV1 = dV2 = 0 dN k1 = ! dN k 2 " 0 dNi1 = dNi 2 = 0 for all i ! k

(rigid wall) (semipermeable wall) (semipermeable wall)

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

! ("1 ... "r , Xr +1 ... X M ) = Y [ X1 ,... Xr ] = Y # $ "i Xi

At equilibrium for the combined system and reservoir:

d 2 E + E ( r ) = d 2 E + ! (j r )d 2 X (j r ) = d 2 E " ! j d 2 X j = d 2 E # $Xj % &

at constant entropy S and pressure p at constant temperature T and pressure p

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

dF = ! S dT ! p dV + " i i dNi dG = ! S dT + V dp + " i i dNi

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

1 $ #V ' 1 $ #v ' = " V& v& % # p) (T % # p) (T

" !s % " !q % T " !S % = T = $ N$ # !T ' &p # !T ' &p $ # !T ' &p

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

Thermodynamics THERMODYNAMIC DERIVATIVES Useful Differential Expressions If z ( x, y ) is constant:

and therefore: " !x% " !z % = ( $ $ # !y' &x # !y' &z

" !z % " !y% = 1 $ $ # !x' &y # !x' &z

Besides, if ! ( x ( w ) , y ( w ) , z ( w )) and z are both constant, differentiating w.r.t. w :

$ "# ' ! & % "y ) ( x,z

$ "# ' $ "x ' = * & & % "x ) ( y, z % "w ) (z

$ "y ' & % "w ) (z

Thus, eliminating ! from these equations:

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

*" ! p % " !p% = Nc p dT ( TV) p ,$ ' dT + $ dV / ' # !V & T +# ! T & V .

TV) p " ! p % TV) p ( ! V ! T ) p )2 T " !S % p cv = $ ' = c p ( = cp + = c p ( Tv $ ' N # !T & V N # !T & V N ( ! V ! p )T *T

Isentropic Compressions and Expansions With the above procedure:

$ #V ' & % #T ) (p/ .

0p cv $ # V ' cv $ #T ' = " = ! = ! " Tv & T T % #V ) (p % #p) ( T cp Vc p & cp

Luca dAgostino, Dipartimento di Ingegneria Aerospaziale, Universit di Pisa, 2010/11.

Thermodynamics THERMODYNAMIC DERIVATIVES Free Expansions No work nor heat exchanges:

) " !V % +p + T$ ' # &p ! T *

" !T % " !H% = ( $ $ # !p ' &T # ! p' &H = v / pT ( 1 cp