CHEM271 - Spring 13 - March 13

Lecture March 13
1
Chapter 14 - Gibbs Free Energy
Remember: Chapter 14 HW and Quiz due
Tuesday, March 26th
All regrade requests must be
submitted by Friday, March 15th!
Chapter 16 Sec. 16.9 and 16.10
CHEM271 - Spring 13 - March 13
Summary of Entropy
2
!Suniverse = !Sreaction - !H/T
!Ssys + !Ssurr
Eq 14.8
Rearranging:
-T!Suniv = !H - T!Sreact
!G
OR
!G =!H - T!S
!G < 0 reaction spontaneous
!G > 0 reaction not spontaneous
!G = 0 reaction is in equilibrium
Note: signs
inverted from !S!!
CHEM271 - Spring 13 - March 13
Calculating !G
o
-

Part

II
3
Use the standard values of formation
!G
o
to calculate !G
o
for a reaction
CaCO3(s) " CaO(s) + CO2(g)
Analogous to !H
o
of
formation
!G
o
= #!G
o
(products) - #!G
o
(reactants)
!G
o
= [(-603.3) + (-394.4)] - (-1128.8)
= +131.1 kJ
Positive so reaction is NOT spontaneous at 25
o
C.
T = 298.15 K
Pressure =1 atm
CHEM271 - Spring 13 - March 13
Temperature Dependence of !G
4
CaCO3(s) " CaO(s) + CO2(g)
!G
o
=!H
o
- T!S
o

!G
o
> 0 Reaction NOT spontaneous (at 25
o
C)
If you assume that !S and !H at di$erent temperatures
can be estimated by their values at 25
o
C, then can
calculate T when reaction becomes spontaneous "
Set !G =0 = !H
o
- T!S
o
T = !H/!S = (178.5)/(.1588) =1124 K
so T >1124 K reaction is spontaneous
Same T
as
before
CHEM271 - Spring 13 - March 13
Analyzing a System in
Terms of Sign of !H and !S
5
!
exothermic
!
spontaneous at
LOW T
! +
Always
spontaneous
+ endo !
Never
spontaneous
+ +
spontaneous at
HIGH T
!H !S !G = !H -T!S
CHEM271 - Spring 13 - March 13
Qualitative Example
6
Given the reaction can determine the sign
of !S
Given that the reaction is exothermic
Consider the reaction
2NO(g) + 2H2(g) " N2(g) + 2H2O(g)
4 moles of gas to 3 moles of gas
-
Reaction will be spontaneous (!G<0) at
LOW temperature
!H is
-
!G = !H -T!S
CHEM271 - Spring 13 - March 13
Example of AgCl
7
Ag
+
(aq) + Cl
-
(aq) AgCl(s)
!H
o
= -65.5 kJ/mol
!S
o
= -33.0 J/molK
!G
o
= (-65.5) - (298.15)(-.0330) = -55.7 kJ/mol
at 25
o
C
Will get the same value if you use the
!G
o
values from Table A4.3
What if you increased the T to 100.
o
C?
EXOTHERMIC
!G
o
= (-65.5) - (373)(-.0330) = -53.2 kJ/mol
Remember [Ag
+
] and [Cl
-
] = 1 M
Balance T
= 1980 K
CHEM271 - Spring 13 - March 13
Non-Standard
Conditions Sec. 16.9
8
where Q is the reaction quotient
Eq 16.25
R is the gas constant in energy units =
8.3145 J/(molK)
!G = !G
o
+ RTlnQ
CHEM271 - Spring 13 - March 13
AgCl at Non-Standard
Conditions
9
What if [Ag
+
] = 1.0 x 10
-6
and [Cl
-
] = 2.2 x 10
-6
Ag
+
(aq) + Cl
-
(aq) AgCl(s)
Q = 1/(1.0x10
-6
)(2.2x10
-6
) = 4.5 x 10
11
Note: reverse of Ksp
!G = -53.0 + (.008315)(373)(26.84)
= +30.2 kJ
Using T= 100.
o
C
lnQ = 26.84
NOT Spontaneous - no ppt
CHEM271 - Spring 13 - March 13
Quiz of the Day
10
Use the accompanying thermodynamic data for the
formation of CCl4(g) via the hypothetical reaction of
C(s) + 2Cl2(g) CCl4(g)
!H
o
(kJ/mol) S
o
(J/mol-K)
CCl4(g) -102.9 309.7
C(s) 5.7
Cl2(g) 223.0
If you are at standard
pressures of 1 atm, what
is !G
o
for this reaction at
50.0
o
C?
Ans:
!G
o
= !H
o
- T!S
o
!H
o
= -102.9 kJ
!S
o
= 309.7 - {5.7+2(223.0)} =
-142.0 J/K
!G = -102.9 - (323.15)(-.1420)
= -102.0 + 45.9 = -57.0 kJ