CHEMICAL THERMODYNAMICS

The first law of thermodynamics:

Energy and matter can be neither created nor destroyed;
only transformed from one form to another. The energy
and matter of the universe is constant.
The second law of thermodynamics:
In any spontaneous process there is always an increase in the
entropy of the universe. The entropy is increasing.
The third law of thermodynamics:
The entropy of a perfect crystal at 0 K is zero. There is no
molecular motion at absolute 0 K.

STATE FUNCTIONS
A property of a system which depends only on its present state
and not on its pathway.
H - Enthalpy - heat of reaction - qp
A measure of heat (energy) flow of a system relative to its
surroundings.
H standard enthalpy
Hf enthalpy of formation
H = n Hf (products) - m Hf (reactants)
H = U + PV
U represents the Internal energy of the particles, both the
kinetic and potential energy. U = q + w

HEAT

VS

WORK

energy transfer as a
result of a temperature
difference

energy expanded to
move an object against
a force

qp

w=Fxd

endothermic (+q)

work on a system
(+w)

exothermic (-q)

work by the system

(-w)

qc = -qh

w = -PV

SPONTANEOUS PROCESSES
A spontaneous process occurs without outside intervention.
The rate may be fast or slow.
Entropy
A measure of randomness or disorder in a system.
Entropy is a state function with units of J/K and it can be
created during a spontaneous process.
Suniv = Ssys + Ssurr
The relationship between Ssys and Ssurr
Ssys
Ssurr
Suniv
Process spontaneous?
+
+
+
Yes
No (Rx will occur in
opposite direction)
+
?
Yes, if Ssys > Ssurr
+
?
Yes, if Ssurr > Ssys

Entropy
S = Sf - Si

S > q/T

S = H/T
For a reversible (at equilibrium) process
H - T S < 0
For a spontaneous reaction at constant T & P
H - T S
If the value for H - T S is negative for a reaction then the
reaction is spontaneous in the direction of the products.
If the value for H - T S is positive for a reaction then the
reaction is spontaneous in the direction of the reactants.
(nonspontaneous for products)

Formula
Nitrogen
N2(g)
NH3(g)
NO(g)
NO2(g)
HNO3(aq)
Oxygen
O2(g)
O3(g)
42.7
OH-(aq)
H2O(g)
H2O(l)

S,
J/(molK)

Formula

191.5
193
210.6
239.9
146

Sulfur
S2(g)
S(rhombic)
S(monoclinic)
SO2(g)
H2S(g)

205.0
238.8

Fluorine
F-(aq)
F2(g)

-10.5
188.7
69.9

HF(g)
Chlorine
Cl-(aq)
Cl2(g)
HCl(g)

S,
J/(molK)

Formula

228.1
31.9
32.6
248.1
205.6

Bromine
Br-(aq)
Br2(l)
Iodine
I-(aq)
I2(s)

-9.6
202.7
173.7
55.1
223.0
186.8

S,
J/(molK)
80.7
152.2
109.4
116.1

Silver
Ag+(aq)

73.9
Ag(s)

AgF(s)
AgCl(s)
AgBr(s)
AgI(s)

84
96.1
107.1
114

S,
Formula
Hydrogen
H+(aq)
H2(g)
Sodium
Na+(aq)
Na(s)
NaCl(s)
NaHCO3(s)
Na2CO3(s)
Calcium
Ca2+(aq)
Ca(s)
CaO(s)
CaCO3(s)

J/(molK)
0
130.6
60.2
51.4
72.1
102
139
-55.2
41.6
38.2
92.9

S,
Formula
Carbon
C(graphite)
C(diamond)
CO(g)
CO2(g)
HCO3-(aq)
CH4(g)
C2H4(g)
C2H6(g)
C6H6(l)
HCHO(g)
CH3OH(l)
CS2(g)
CS2(l)
HCN(g)

J/(molK)
5.7
2.4
197.5
213.7
95.0
186.1
219.2
229.5
172.8
219
127
237.8
151.0
201.7

S,
Formula

J/(molK)

Carbon (continued)
HCN(l)
112.8
CCl4(g)
309.7
CCl4(l)
214.4
CH3CHO(g)
266
C2H5OH(l)
161
Silicon
Si(s)
18.0
SiO2(s)
41.5
SiF4(g)
285
Lead
Pb(s)
64.8
PbO(s)
66.3
PbS(s)
91.3

S = Standard Entropy = absolute entropy

S is usually positive (+) for Substances
S can be negative (-) for Ions because H3O+ is used as
zero
Predicting sign of S (+) cases
l. Rx in which molecule broken
2. Rx where increase in mol of gas
3. Process where s l or sg or lg
S = n S (P) - m S (R)

APPLICATION OF THE 3RD LAW OF THERMODYNAMICS

S = standard entropy
= absolute entropy
Predicting the sign of S
The sign is positive if:
1. Molecules are broken during the Rx
2. The number of moles of gas increases
3. solid liquid
liquid gas
solid gas
an increase in order occurs
1. Ba(OH)2 8H2O + 2NH4NO3(s) 2NH3(g) + 10H2O(l) +
Ba(NO3)2(aq)
2. 2SO(g) + O2(g) 2SO3(g)
3. HCl(g) + NH3(g) NH4Cl(s)
4. CaCO3(s) CaO(s) + CO2(g)

 S = n S (product) - m S (reactant)
1.

Acetone, CH3COCH3, is a volitale liquid solvent.

The standard enthalpy of formation of the liquid at
25 C is -247.6 kJ/mol; the same quantity for the
vapor is -216.6 kJ/mol. What is S when 1.00 mol
liquid acetone vaproizes?

2.

Calculate S at 25 for:
a. 2 NiS(s) + 3 O2(g) 2 SO2(g) + 2 NiO9(s)
b. Al2O3(s) + 3 H2(g) 2 Al(s) + 3 H2O(g)

GIBBS FREE ENERGY : G

G = H - TS
describes the temperature dependence of spontaneity
Standard conditions (1 atm, if soln=1M & 25):
G = H - TS
A process ( at constant P & T) is spontaneous in
the direction in which the free energy decreases.
1. Calculate H, S & G for
2 SO2(g) + O2(g) 2 SO3(g) at 25C & 1 atm

Formula

Gf
kJ/mol

Nitrogen
N2(g)
NH3(g)
NO(g)
NO2(g)
HNO3(aq)

Sulfur
0
-16
86.60
51
-110.5

Oxygen
O2(g)
O3(g)
OH-(aq)
H2O(g)
H2O(l)

Formula

Gf
kJ/mol

S2(g)
S (rhombic)
S (monoclinic)
SO2(g)
H2S(g)

Bromine
80.1
0
0.10
-300.2
-33

Fluorine
0
163
-157.3
-228.6
-237.2

F-(aq)
F2(g)
HF(g)

Br-(aq)
Br2(l)

-102.8
0

Iodine
I-(aq)
I2(s)

-51.7
0

Silver
-276.5
0
-275

Chlorine
Cl-(aq)
Cl2(g)
HCl(g)

Formula

Gf
kJ/mol

-131.2
0
-95.3

Ag+(aq)
Ag(s)
AgF(s)
AgCl(s)
AgBr(s)
AgI(s)

77.1
0
-185
-109.7
-95.9
-66.3

Formula

Gf
kJ/mol

Hydrogen
H+
0
H2(g)
0
Sodium
Na+(aq)
-261.9
Na(s)
0
NaCl(s)
-348.0
NaHCO3(s)
-851.9
Na2CO3(s)
-1048.1
Calcium
Ca2+(aq)
-553.0
Ca(s)
0
CaO(s)
-603.5
CaCO3(s)
-1128.8

Formula
Carbon
C (graphite)
C (diamond)
CO(g)
CO2(g)
HCO3-(aq)
CH4(g)
C2H4(g)
C2H6(g)
C6H6(l)
HCHO(g)
CH3OH(l)
CS2(g)
CS2(l)
HCN(g)

Gf
kJ/mol

0
2.9
-137.2
-394.4
-587.1
-50.8
68.4
-32.9
124.5
-110
-166.2
66.9
63.6
125

Formula
Carbon (cont.)
HCN(l)
CCl4(g)
CCl4(l)
CH3CHO(g)
C2H5OH(l)
Silicon
Si(s)
SiO2(s)
SiF4(g)
Lead
Pb(s)
PbO(s)
PbS(s)

Gf
kJ/mol

121
-53.7
-68.6
-133.7
-174.8
0
-856.6
-1506
0
-189
-96.7

STANDARD FREE ENERGY OF FORMATION

Gf
The free energy change that occurs when 1 mol of
substance is formed from the elements in their standard
state.
Calculate G for:
2 CH3OH(g) + 3 O2(g) 2 CO2(g) + 4 H2O(g)

INTERPRETING G FOR SPONTANEITY

1.

When G is very small (less than -10 KJ) the reaction

is spontaneous as written. Products dominate.
G < 0

2.

G(R) > G(P)

When G is very large (greater than 10 KJ) the reaction

is non spontaneous as written. Reactants dominate.
G > 0

G(R) < G(P)

3.

When G is small (+ or -) at equilibrium then both

reactants and products are present.
G = 0

Q:

Ba(OH2) 8 H2O(g) + 2 NH4NO3(g) 2 NH3(g) +

10 H2O(l) + Ba(NO3)3(aq)

G AND EQUILIBRIUM
The equilibrium point occurs at the lowest free energy
available to the reaction system.
When a substance undergoes a chemical reaction, the reaction
proceeds to give the minimum free energy at equilibrium.
G = G + RT 1n (Q)
at equilibrium: G = 0
G = -RT 1n (k)
G = 0
then K = 1
G < 0
then K > 1
G > 0
then K < 1
Q: Corrosion of iron by oxygen is
4 Fe(s) + 3 O2(g) 2 Fe2O3(s)
calculate K for this Rx at 25C.

1. Calculate G at 25c
Ba SO4 (s) Ba2+(aq) + SO42-(aq)
What is the value for Ksp at 25C?
2. Calculate K for
Zn(s) + 2H+(aq) Zn2+(aq) + H2 (g) at 25c.

G & Spontaneity is dependent on Temperature

GT = H - T S

Spontaneous at all T

Non spontaneous at all T

+/-

At Low T= Spontaneous
At High T= Nonspontaneous

+/-

At low T= Nonspontaneous
At High T= Spontaneous

Q.
Predict the Spontaneity for H2O(s) H2O(l) at -10c ,
0c & 10c.

1. At what temperature is the following process spontaneous at

1 Atm?
Br2 (l) Br2 (g)
What is the normal boiling point for Br2 (l)?
2. Calculate G & Kp at 35c
N2O4 (g) 2 No2 (g)
3. Calculate H, S & G at 25c and 650c.
CS2 (g) + 4H2 (g) CH4 (g) + 2H2S(g)
Compare the two values and briefly discuss the
spontaneity of the Rx at both temperature.