Department o C emist

Dependence ofState Functions on Variables: (Variables T ,P and V)

Internal Energy (Variables V and T)
First law : dU = 8q + 8w dU = TdS - PdV ....... (1) ·. · 8q = TdS

au) =r(~)
(av rav r
-P ........... (2) and 8w= -PdV

We know, Helmohltz free energy A=V-TS. ....... (3)

Differetiating eq(3) we get, dA = dU -TdS-SdT
dA =TdS-PdV-TdS - SdT j·:dU=TdS-PdV
dA=-PdV-SdT. ........ ~) Con1paring eq(4) and (S) we get,

Again A= f(V , T) aA) =-P

(av (aA) =-S
r or "
:.dA= ( -aA) dV+ (aA)
- dT......(5) -a-A
2

= {aP)
- aA2
_( as)
av r ar v avar ar v arav--lav r

.·.(aP)
ar
=(v
as)
av r
... . . ( 6) Cross derivative;

Now from eqn(2) and(6)weget,

 Department of Chemist
Dependence of State Functions on Variables .. .. ...... .
Enthalpy (Variables P and T)
First law: dU==&j+&v dU==TdS-PdV ....... (1) ·:&,_==TdS
H == U + PV ....... ( 2) and.iw==-PdV
Differentiation of eq(2) gives dH ==dU + PdV + VdP ......... (3)
From eq(l) and (3) we get, dH == VdP+ TdS ..........(4)
Differentiating eq(4) w. r. to Pat canst. T, we get

:.(BH)
BP
== V+ ,,.£ dS) ......... (s)
T .l\dP T

Weknow, dG==VdP-SdT
iJG) ==-S
(or p
and (BG)
BP
== V
T

:r(:)={!\ CrossDerNatwes !(:~)=(:;l

(!;l ={!l-······<6)
Fromeq(S)and{6}we get,
 Dependence of State Functions on Variables .... ... ......

Fromeqn(S) and(6): (~!\ =v-1!~)P

[Thermodynamic Eqn of state for H]

BH) ==V-TnR Idealgasequation:PV==nRT

( BP T p

:-(~!l =O :-(~;\ =n:

.·. Enthalpy of an Ideal Gas is Independant of Pressure
and Depends only on Temp

st nd
1 ,2 andeross D er1va
. tives
f(x,y) ==x 2 +5xy+2y2
df
f == df ==2x+5y f ==-==5x+4y
,, dy
x dx
d2f
d2f
f xy ==-==5 fn,-✓ == lvr ==5 fyx = dydx =5
dxdy ✓-
 , Department of Chemistry
'

dG for Reactions: Gibbs- Helmholtz equation

We know, AG=AH-TAS---(1)
AG is a function of T and P

.-.d(AG>=la~G)l dT+la~PG)l dP---(2)

Differentiating eq(l) w. r. to Tat constant P we get,

l oTP =lo<AH>]
o(AG)] -rla<AS>]
ofP ofP
-AS---(J)

[o(AS)]
[ a(AG)] =AC -TACP AS ·.-[o(AH)] =AC and = ACP
or p p T ar p p oT p T

.-[o(AG)]
. oT _ ........(4)
--ASp

From eq ( 1) and (3) we get,

o(AG)]
AG = AH + T [ ~ OT p •••••• ( 4)
 From eq (1) and (3) we get, AG== AH+ T[o(AG)l ······(4)
oT P

. . AG rto T we get
D1•ffierentiating-w. o(A<Jf)] =r[o(AG¼r]-AG
T [ oT p y2
a(AGA)] =AG-AH-AG From eqn (4) :
[ oT p T 2

r[o(AG)] =AG-AH
oT p
8(A<½)] =-AH
[ BT p T
2

d(AG)= -AH dT r2 ,1 AG)=-rT2 ~ T

T Tl J1 "'\ T J¾ Tl
 Department of Chemistry

Problem: The overall reaction for the metabolic breakdown of

glucose in our bodies is the same as combustion of glucose in air.
Using the data given below, determine whether the reaction will be
more favored at 37°C. Given: /1G = -2878.92 kJ and 11H° = -2801.65
0

kJ at 298K ~ AG; = -2882.03 kJ