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6 Maxwelleq

1) The document discusses fundamental equations of thermodynamics including the 1st and 2nd laws of thermodynamics and equations for internal energy, enthalpy, Helmholtz energy, and Gibbs energy. 2) It defines chemical potential and several Maxwell relations. 3) For spontaneous processes, the internal energy, enthalpy, Helmholtz energy, and Gibbs energy must decrease under conditions of constant entropy, volume, pressure, temperature, and moles of substances.

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Christopher Jordan Evoniuk
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189 views7 pages

6 Maxwelleq

1) The document discusses fundamental equations of thermodynamics including the 1st and 2nd laws of thermodynamics and equations for internal energy, enthalpy, Helmholtz energy, and Gibbs energy. 2) It defines chemical potential and several Maxwell relations. 3) For spontaneous processes, the internal energy, enthalpy, Helmholtz energy, and Gibbs energy must decrease under conditions of constant entropy, volume, pressure, temperature, and moles of substances.

Uploaded by

Christopher Jordan Evoniuk
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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FUNDAMENTAL EQUATIONS OF THERMODYNAMICS MAXWELL EQUATIONS 1st law dU=dq+dw 2nd law

dS>dq /T in an irreversible process dS=dqrev /T in an reversible process

INTERNAL ENERGY FOR A CLOSED SYSTEM WITH ONLY REVERSIBLE MECHANICAL WORK:

dU = dq PdV

and

dq = TdS

dU = TdS PdV

Fundamental equation of U for a closed system involving only mechanical work. U is a function of S and V and dU is an exact differential, so it can be written as:

Then

# U & # U & dU = % ( dS + % ( dV . $ S 'V $ V ' S

# U & T =% ( $ S 'V

$ U ' P = & ) % V ( S

Since dU is an exact differential it follows that

# T & # P & % ( = % ( $ V ' S $ S 'V


this is a Maxwell relation.

INTERNAL ENERGY FOR A CLOSED SYSTEM WITH ONLY IRREVERSIBLE MECHANICAL WORK:
For an irreversible, spontaneous, process

dq TdS so that

dU TdS Pext dV

A change can take place spontaneously at constant entropy and volume only if the internal energy decreases.

(dU) S,V 0

INTERNAL ENERGY FOR AN OPEN SYSTEM


In an open system there is transfer of matter that corresponds to chemical work: for specie i equal to i dni.

dU = TdS PdV + 1dn1 + 2 dn 2 + ...+ N dn N


N # # U & # U & U & dU = % ( dS + % ( dV + % ( dn i $ S 'V ,{ n } $ V ' S,{ n } i=1 $ n i ' S,V ,{ n j i }

# U & where the chemical potential is defined as i = % n ( $ i ' S,V ,{ n j i } .


For an irreversible, spontaneous, process

dq TdS so that

% U ( dU TdS Pext dV + ' * dn i i=1 & n i ) S,V ,{ n j i }


A change can take place spontaneously at constant entropy, volume and number of moles, only if the internal energy decreases.

(dU) S,V ,{n i } 0


At constant values of T, P, and , we can integrate dU to obtain:
N

U = TS PV + i n i
i=1

It is difficult to keep S and V constant U is not a useful way of representing energy.

ADDITIONAL THERMODYNAMIC POTENTIALS


Enthalpy:

H=U+PV
dH = dU + PdV + VdP dH = TdS + VdP
N

dH = TdS + VdP + i dn i
i

where the chemical potential is defined as

# H & i = % ( $ n i ' S,P ,{ n j i } and

# H & # H & T =% ( ,V = % ( $ S ' P,{n i } $ P ' S,{n i } .

Maxwell relation:

# T & # V & =% ( % ( $ P ' S,{n i } $ S ' P,{n i }

A change can take place spontaneously at constant entropy, pressure and number of moles, only if the enthalpy decreases.

(dH) S,P,{n i } 0
N i=1

(P = Pext )

Integrated: H = TS i n i .

Helmholtz energy:

A=U-TS

dA = dU TdS SdT dA = PdV SdT


N

dA = PdV SdT + i dn i
i

# A & i = % ( where the chemical potential is defined as and $ n i 'V ,T ,{ n j i }

$ A ' $ A ' S = & ) ,P = & ) . % T (V ,{n i } % V (T ,{n i }

A change can take place spontaneously at constant volume, temperature, and number of moles, only if the Helmholtz energy decreases.

(dA)T ,V ,{n i } 0.
# S & # P & =% ( % ( $ V 'T ,{n i } $ T 'V ,{n i }
N

Maxwells relation:

Integrated: A = PV + i n i .

i=1

Gibbs energy:

G=H-TS

dG = dH TdS SdT dG = TdS + VdP TdS SdT = VdP SdT


N

dG = SdT + VdP + i dn i
i

where the chemical potential is defined as

# G & i = % ( $ n i 'T ,P ,{ n j i }

and

# G & i = % ( is $ n i ' S,P ,{ n j i }

$ G ' $ G ' S = & ) ,V = & ) . % T ( P ,{n i } % P (T ,{n i }


also called the partial molar Gibbs energy i = G i .

If a thermodynamic potential (e.g. G) is known as a function of its natural variables, we can calculate all of the thermodynamic properties of the system:

Entropy and Volume from partial derivative of G; since G = U + PV TS = H TS , then:

$ G ' $ G ' U = G PV + TS = G P& ) T& ) % P (T % T ( P $ G ' H = G + TS = G T& ) % T ( P $ G ' A = G PV = G P& ) % P (T

A change can take place spontaneously at constant pressure, temperature, and number of moles, only if the Gibbs energy decreases.

(dG)T ,P,{n i } 0 (T = Tsurr , P = Pext ).


At constant T, P, and i
N

G = i n i
i=1

Maxwells relation: $ S ' $ V ' & ) =& ) , % P (T {n i }, % T ( P,{n i }

$ S ' $ ' & ) =& i) = Si , the partial molar entropy % n i (T ,P,{n j ii }, % T ( P ,{n i }

# V & # & =% i( = Vi % ( , the partial molar volume. n i 'T ,P ,{n }, $ P 'T ,{n i } $ j ii

At constant T and P a spontaneous process will occur with an increase of the total entropy and a decrease of the Gibbs energy.

Ssystem + Ssurroundings > 0 H system T TSsystem H system > 0 Ssurroundings = G > 0 G < 0

Even if G<0, a process still can be kinetically unfavorable.

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