Thermodynamic Relationships

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

FFF1

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

FFF3

FFF2

" !x % " !x % " !x % " !z % $ ' = $ ' +$ ' $ ' $ ' $ ' $ ' # !y & w # !y & z # !z & y # !y & w

FFF4

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Internal Energy U = U(S,V,N) dU = TdS " pdV + dN # "U & # "U & # "U & % ( =T % ( = )p % ( = $ "S 'V ,N $ "V ' S,N $ "N ' S,V Maxwell Relations # "T & # "p & # "T & # " & $ #p ' $ # ' "& ) = & ) % ( = )% ( % ( =% ( $ "V ' S,N $ "S 'V ,N $ "N ' S,V $ "S ' N ,V % #N (V ,S % #V ( N ,S ! ! Equivalently: Entropy S = S(U,V,N) ! dS = "dU + !pdV # "dN " # "S & # "S & # "S & 1 % ( =) = % ( = )p % ( = )* $ "U 'V ,N $ "V 'U ,N $ "N 'U ,V kB T Maxwell Relations $ "# ' $ "#p ' $ "# ' $ " ' $ "#p ' $ "# ' & ) =& ) & ) = *& ) & ) = *& ) % "V (U ,N % "U (V ,N % "N (U ,V % "U ( N ,V % "N (V ,U % "V ( N ,U ! ! Helmholtz Free Energy ! ! F = U " TS = F(T,V,N) dF = "SdT " pdV + dN # "F & # "F & # "F & % ( = )S % ( = )p % ( = $ "T 'V ,N $ "V 'T ,N $ "N 'T ,V Maxwell Relations # "S & # "p & # "S & # " & # "p & # " & % ( =% ( % ( =% ( % ( = )% ( $ "V 'T ,N $ "T 'V ,N $ "N 'T ,V $ "T ' N ,V $ "N 'V ,T $ "V ' N ,T ! ! Gibbs Free Energy ! ! G = F + pV = U " TS + pV = G(T, p,N) = N(T, p) dG = "SdT + Vdp + dN # "G & # "G & # "G & % ( = )S % ( = % ( =V $ "T ' p,N $ "N 'T , p $ "p 'T ,N

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Maxwell Relations # "S & # "S & # " & # "V & % ( = )% ( % ( = )% ( $ "T ' N , p $ "T ' p,N $ "N 'T , p $ "p 'T ,N d = "sdT + vdp # " & # " & )S V % ( = )s = % ( =v = $ "T ' p,N $ "p 'T ,N ! N ! N Maxwell relation for # "s & # "v & % ( = )% ( $ "T ' p $ "p 'T !

# " & # "V & % ( =% ( $ "N ' p,T $ "p ' N ,T

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Thermodynamic Potential " = #F + N = #U + TS + N = "(T,V, ) = Vp(T, ) d" = SdT + pdV + Nd $ "# ' $ "# ' $ "# ' & ) =S & ) =p & ) =N % "T (V , % "V (T , % " (T ,V Maxwell Relations # "S & # "p & # "S & # "p & # "N & # "N & % ( =% ( % ( =% ( % ( =% ( $ "V 'T , ! $ "T 'V , $ " 'T! $ "T ' ,V $ " 'V ,T $ "V ' ,T ,V dp = sdT + nd # "p & # "p & S N % ( =s= % ( =n= $ "T 'V , ! V V $ " 'T! ,V Maxwell Relation for p # "s & # "n & % ( =% ( $ " 'T ,V $ "T ' ,V ! Magnetic Free Energy A = U(S, M) " TS = A(T, M,N) dA = "SdT + HdM # "A & # "A & % ( = )S % ( =H $ "T ' M $ "M 'T Maxwell Relations # "S & # "H & % ( = )% ( $ "M 'T $ ' ! "T M Magnetic Free Energy F = A " HM = U " TS " HM = F(T,H) dF = "SdT " MdH # "F & # "F & % ( = )S % ( = )M $ "T ' H $ "H 'T

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Maxwell Relations # "S & # "M & % ( = )% ( $ "H 'T $ "T ' H Common thermodynamic second derivatives. These are all nonnegative because of the second law of thermodynamics. Heat Capacity at constant volume # " 2F & # "S & CV = T% ( = )T% 2 ( * 0 $ "T 'V $ "T 'V All other heat capacities such # "S & # "S & # "S & C p = T% ( ) 0 , C H = T% ( ) 0 and CM = T% ( ) 0 $ "T ' H $ "T ' M $ "T ' p are also non-negative. Isothermal Compressibility "1 $ #V ' 1 $ #n ' 1 $ #n ' 1 $# 2 p ' ! ! KT = & ) = & ) = 2 & ) = 2 & 2 ) * 0 V % #p (T n % #p (T n % # (T n % # (T Isothermal Susceptibility $ #M ' 1 "T = & *0 ) = % #H (T $ #H ' & ) % #M (T Microcanonical partition function "(U,V,N) = trace(# #U (H $ U)) = number of states in small energy range near U S(U,V,N) = ln("(U,V,N)) Canonical partition function

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Z(T,V,N) = trace(exp("#H)) = % e" #U $(U,V,N) =

U

1 N!h 3N

&d

r r pd N r e" #H

F(T,V,N) = "kB T ln(Z(T,V,N))

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Grand canonical partition function

%

"(T,V, ) = trace(exp(#$H + $N)) = & e $N Z(T,V,N)

N= 0

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"(T,V, ) = k B T ln(#(T,V, )) = Vp(T, ) k T p(T, ) = B ln("(T,V, )) V

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Isobaric partition function Y (T, p,N) = trace(exp("#H " #pV )) = $ dV e" #pV Z(T,V,N) G(T, p,N) = "kB T ln(Y (T, p,N)) = N(T, p) k T (T, p) = " B ln(Y (T, p,N)) N

Clausius-Clapyron Equation dp" s2 # s1 L = = dT v 2 # v1 T (v 2 # v1 ) where p" (T) is the coexistence pressure curve between two phases, s is the entropy per particle of the phases, v is the volume per particle of the phases and L is the latent heat of transformation.
! Statistical Relations for some common thermodynamic first derivatives $ "#F ' trace( He* #H ) U =& = H = E energy ) = trace(e* #H ) % "# (V ,N

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# "p & trace( Ne) *H + *N ) N n =% ( = = V trace(e) *H + *N ) $ " 'T ,V trace( Me" *E ) $ #F ' M = "& ) = = M % #H (T ,N trace(e" *E )

density magnetization

Statistical Relations that relate thermodynamic second derivatives to variances 2 # " 2F & E2 ) E # "S & CV = T% ( = )T% 2 ( = *0 $ "T 'V kB T 2 $ "T 'T

N2 ) N 1 # "n & 1 #" 2 p & KT = 2 % ( = 2 % 2 ( = n $ " 'T n $ " 'T VkB T ! ! ! $ # 2F ' M2 * M $ #M ' "T = & ) = *& 2 ) = % #H (T kB T % #H (T
2

2 1 N ) N = nk B T N

= KT

ideal

N2 ) N N

*0

+0