U-H-F-G

energy
Total energy of a system: Etot = Epot*) + Ekin) + U
this is conventional physics internal energy is a thermodynamic concept

*) energy of postiton in any type of conservative field ) energy of motion relative to a given inertia system

bilinearity of energy
Let Z = Z ( X , Y ) be a thermodynamic function of state. Variables X , Y form bilinear terms X Y with [ X Y ] = [energy] : heat T S ; work P V . Note that P and V may represent generalized work variables; generalized work = generalized force generalized path L : r r Wmech = F x ; W = Am M ; r r Wel = z F ; Wmag = H M ; etc.

Note that for molar functions Z , V V M in [cm3 / mol ]. Thus V V M = M

and dV dV M

dV M d = 2 d M = V M

state and process functions

The value of a thermodynamic function of state Z(X,Y) depends on the variables X, Y only, no matter, how the state is reached. The following statements are equivalent: Z is a function of state. The value of Z is path-independent. The differential dZ is a complete differential. Z is an integrable function.
II

The value of the integral on the path I II.

dZ = Z II Z I
I

does not depend

state and process functions

Example: internal energy

dU = Q + W

Q = heat transferred to the system W = work performed on the system

II

Note that

dU = U II U I
I

II

while

Q = QI , II
I

II

and

W = WI , II .
I

function of state There is no such thing like QI or WI.

process function (energy in transition)

Restoring integrability: dS = Q / T dU = TdS -PdV

cross-differential relation

c.d.r.
Z = Z ( X ,Y )
II

Let Z be integrable :

dZ =Z ( II ) Z ( I )
I

with

Z Z dZ = dX + dY = AdX + BdY X Y Y X Then 2Z 2Z XY = YX A B or = Y X

change-of-variable relation

Z = Z ( X ,Y ) Z Z dZ = dY dX + Y X X Y Z Z 0 = dX + dY Y X X Y Z X Z 0 = + X Y X Z Y X Z = const X Z Y X Z

c.v.r.

Z Y Y X Y Z X = = Z X X Z Y X Z Y

change-of-variable relation

c.v.r.
Y Y Z X = X X Z Z Y

characteristic variables:
The thermodynamic functions U, H, F, G may be expressed as functions of either of the variable pairs T, S or -P, V. For excample, the internal energy U may be expressed as U(T,V), U(T,P), U = U(S,V), U(S,P). But for only one characteristic combination, the differential quotients yields the complementary variables:

U U dU = dS + dV = TdS PdV S V V S
Hence, S and V are the characteristic variables of U.

S H P

V F

A move to the right generates a + sign; a move to the left generates a - sign.

U, H, F, G
Note that U H T = = ; S V S P H G V = ; = P S P T

F G U F S = = ; P = = T V T P V S V T
fundamental energy term; closed system; bomb calorimetry; V = const. processes

U H = U + PV , dH = dU + d ( PV ) F = U TS , dF = dU d (T S ) G = H TS , dG = dH d (T S )

dU = TdS PdV dH ( S , P) = TdS + VdP dF (T , V ) = SdT PdV dG (T , P ) = SdT + VdP

system open to work exchange; calorimetry; P = const. processes

thermal contact; V = const. processes; gas reactions

thermal contact; P = const. processes; classical thermochemistry

U, H, F, G
Use F G S = = T V T P
to derive the Gibbs-Helmholtz equations

F = U TS ( F / T ) F 2 ( F / T ) U = F + TS = F T , = T = T V T V (1 / T ) V G = H TS (G / T ) G 2 (G / T ) H = G + TS = G T = T = T P T P (1 / T ) P

U, H, F, G

F S = T V G S = T P

( F / T ) U = (1 / T ) V
(G / T ) H = (1 / T ) P

F = U TS

G = H TS

P-V-T-S data

P-V-T-S data
S T = cV ; T V 1 V 1 ; = V P T KT 1 V = V ; V T P S T = cP ; T P 1 V 1 ; = V P S KS P = V K T ; T V

V 1 cV , P ~ = ; = cV , P M M
2 cP cV = V

KT T V ;

cV KT 2 ~ ~ cP cV = V KT T / ; = ; cP K S

2 2 T V V T 1 1 V = =~ KT K S cP cP

P-V-T-S data
U U dU = dS + dV = TdS PdV S V V S H H dH = dS + dP = TdS + VdP S P P S F F dF = dT + dV = SdT PdV T V V T G G dG = dT + dP = SdT + VdP P T T P

P-V-T-S data
U U dU = dS + dV = TdS PdV S V V S H H dH = dS + dP = TdS + VdP S P P S

use the c.d.r.

S V = P V T S P S = + T S V P

F F S P dF = dT + dV = SdT PdV = + T V V T V T T V G G dG = dT + dP = SdT + VdP T P P T S V = P T T P

P-V-T-S data
S = P V S = V P S = V T S = P T cV V = T S V K S T cP P = + T S V V T P + = V K T T V V = V V T P
1. Maxwell

2. Maxwell

3. Maxwell

4. Maxwell

 S X Y
Y= P P

X=

cP V V T
0

cP T cV T
0

V
T

cV K T V T

V V

K T V

 V X Y
Y= P P

X=

V V T
cP
0

V V
cV K T V T
0

S
T

K S V
KT V

1 KT V

adiabatic P-V-T processes

S(T,V)

S (T , V ) : S S dS = dT + dV = 0 T V V T cV dS = dT + V KT dV = 0 T

V KT V V V KT V T = = ~ T cV V cV V

adiabatic P-V-T processes

S(T,P)

S (T , P) : S S dS = dT + dP = 0 T P P T cP dS = dT V V dP = 0 T

V T V V = P = ~ P T cP cP

adiabatic P-V-T processes

S(P,V)

S ( P, V ) : S S dS = dV + dP = 0 V P P V cV cP dS = dP + dV = 0 KT V T V V T cV V 1 = P = P V cP KT KS

U(T,V)

dU = TdS PdV
insert dS = dS(T,V):

dU = cV dT + (V KT P ) dV

U T P
dH = TdS + VdP
insert dS = dS(T,P):

U V T

H(T,P)

dH = cP dT + (1 V ) V dP

H T P

H P T

cV and cP
cV dS (T , V ) = dT + V KT dV T cP dS (T , P) = dT V V dP T cP cV 0= dT V V dP V KT dV T cP cV 0= T T P V V V KT T P T P 1
2 cP cV = V KT V T > 0

+ T P V T P

V V

quantity M n 0 VM V KS KT cP cV 3 n R cP cV cP/cV KS/KT [g/mol] [0] [g/cm3] [cm3/mol] [10-6 K-1] [MPa] [MPa] [J/(gK)] [J/(gK)] [J/(gK)] [J/(gK)] [0] [0]

NaCl 58.443 2 2.164 27.007 117.52 25,030 23,720 0.865 0.817 0.854 0.048 1.059 1.055

CaF2 78.076 3 3.180 24.552

MgO SiO2 qtz 40.311 2 3.581 11.257 60.084 3 2.649 22.682 34.94 37,700 37,440 0.745 0.740 0.958 0.005 1.007 1.007

60.65 30.90 83,860 162,260 81,170 160,020 0.879 0.926 0.850 0.913 0.958 0.854 0.029 1.034 1.033 0.013 1.014 1.014

how to assess two independent elastic constants?

sound velocity = elastic modulus density

ut = ul =

GS

KS + 4 G 3 S

1/ 3

3 um = 3 3 2 / ut + 1 / ul

KS

how to assess two independent elastic constants?

K= E E G 2 (1 + ) G = = 3 (1 2 ) 3 (1 2 ) 9G 3E E 3 (1 2 ) 3K E K = = 2 (1 + ) 2 (1 + ) 9 K + E 9K G 3K + G

G=

E = 3 (1 2 ) K = 2 (1 + ) G =

E 1 3K 2G 1 E = + = 1 2 3K + G 2 6 K 2G

Rouxel 2007