Comprehension

One of the problem with entropy calculations is to work out two entropy changes , the change in the
system & change in the surrounding and then consider the sign of their sum. J.W.Gibbs discovered
how to combine the two calculations into one .He focused only on the system. We know,

Suniverse Ssystem Ssurrounding

If enthalpy change of system is H system and any change in surrounding is a reversible process

Suniverse S system

H system

T
T Ssystem H system

Or

T Suniverse

Or

T Suniverse T Ssystem Hsystem Gsystem

Thus for any natural/spontaneous process :

Suniverse 0 or Gsystem 0
Hence ,J.W. gave a new term Gibbs energy(G) which is given as

G H TS .............................(1)
It is a state function and an extensive property.
Standard Gibbs energy of formation G 0f of any element in its standard state is assumed to
be zero
For a chemical reaction:

r G PG 0f ( products) RG 0f (reac tan ts)

Decrease in Gibbs energy of a system can also be defined as maximum useful work obtained
by a system. We know,
dU=dq+dw
or
dU dq (dw)exp (dw)nonexp
or

dU T .dS (dw)exp (dw)nonexp

or

dU T .dS PdV (dw)nonexp

or

(dU PdV ) T .dS (dw)nonexp

or

dH T .dS (dw)nonexp

or

dG ( dw) non exp

For a chemical reaction taking place at non-standard states-

r G r G0 RT ln Q............................(1)
Where Q is reaction quotient
Q.1

From the given table answer the following questions:

Hf)298 (-kCal/mole)
Gf)298 (-kCal/mole)
S298 (-Cal/Kmole)

CO(g)
26.42
32.79
47.3

Reaction: H2O(g) + CO(g) H2(g) + CO2(g)

CO2(g)
94.05
94.24
51.1

H2O(g)
57.8
54.64
?

H2(g)
0
0
31.2

(i)
(iv)

0
Calculate r H298

(ii)

0
Calculate r G298

(iii)

0
Calculate r S 298

0
0
Calculate rU 298
(v)
Calculate S 298
[H2O(g)]
Ans. (i) 9.83 kCal/mole; (ii) 6.81 kCal/mole, (iii) 10.13 Cal / K mole,
(iv) 9.83 kCal/mole, (v) + 45.13 Cal/ K mole

Q.2

For the process H2O (l) (1 bar, 373 K) H2O (g) (1 bar, 373 K), the correct set of
thermodynamic parameters is
(A*) G = 0, S = +ve
(B) G = 0, S = ve
(C) G = +ve, S = 0
(D) G = ve, S = +ve

Q.3

What can be concluded about the values of H and S from this graph?

(A*) H > 0, S > 0

(C) H < 0, S > 0
Q.4

(B) H > 0, S < 0

(D) H < 0, S < 0

Standard entropy of X2, Y2 and XY3 are 60, 40 and 50 JK1mol1, respectively. For the
reaction,

1
3
X 2 Y2 XY3 , H 30kJ
2
2
to be at equilibrium, the temperature will be
(A) 1250 K
(B) 500 K
Q.5

(C*) 750 K

(D) 1000 K

Consider oxidation of iron metal

4Fe(s) 3O2 ( g ) 2Fe2O2 ( s)

Show whether reaction is spontaneous at 25C ?

S Fe
O 87.4 J/k mole
2 3

S Fe
23.3 J/k mole

SO 2 205 J/k mole

H f ( fe2O3 ) 824.2 kj/mole.

Q.6

[Ans. Spontaneous]

Fe metal can be produced as

Fe2O3 (s) 3H 2 ( g ) 2 Fl ( s) 3H 2O( g )

H 98.8 kJ/mole
S 141.5 J/k

(a)
(b)

Q.7.

Is the reaction spontaneous at 25 C.

At what temperature will the reaction spontaneous.
Ans. (a) Yes, spontaneous

Following data apply to the vaporization of Hg.

H vap 58.8 KJ/mole
Svap 92.9 J/K mole
(a)
Does Hg boils at 325 C and 1 atm pressure.

(b) T > 698.23 K

Ans.

(b)
What is normal b.p. of Hg. ?
(a) No (b) 632.93 K

Q.8

Is it worth trying to find a catalyst for this reaction under standard state condition at 25C ?
4 NH3 ( g ) 5O2 ( g ) 4 NO( g ) 6H 2O(l )

Gf ( NO) 86.6 KJ/mole

Gf ( H 2O) 237.2 Kj/mole
Gf ( NH3 ) 16.5 KJ/mole
Ans. We can use catalyst.

Q.9

Compute rG for the reaction H2O (l, 1 atm, 323 K) H2O (g, 1 atm, 323 K)
Given that :

vapH at 373 K = 40.639 kJmol1, CP(H2O, l ) = 75.312 J K1mol1,

Cp (H2O, g) = 33.305 J K1mol1.
Ans.

Q.10

1.683 Kj

2MgO( S ) at 250C is,

The G 0 value for the reaction, 2Mg( S ) O2( g )
0
0
217 JK 1 , Ssurr
(Given Ssys
4 kJK 1 )

A) +3780Jmol-1

B*) -1126 kJmol-1

C) -1192 kJmol-1

D) -3780 kJmol-1