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.