CHEM 1332

THERMODYNAMICS
Definitions:
H
S
G

enthalpy (heat) change at constant pressure can be measured

If ve exothermic
heat given to surroundings (good)
If +ve endothermic heat taken from surroundings (bad)
entropy (randomness) change
If +ve, INCREASE in randomness (good)
If ve, DECREASE in randomness (bad)
Free energy change relates to ideal work from reaction cannot be measured
If ve, SPONTANEOUS reaction (needs no external driving force)
If +ve, NON-SPONTANEOUS (needs external driving force)

Standard State Defined convention; pure liquids or solids; gases at 1 atm; solutions at 1 M
Laws (have not been violated, based on experimental evidence)
1st Law of Thermodynamics Law of Conservation of Energy
2nd Law of Thermodynamics Spontaneous processes must lead to increase in S of universe
3rd Law of Thermodynamics Only perfect crystal at 0 K has zero entropy
Predicting Entropy
1.
2.
3.
4.
5.

Phases
g>l>s
Mixtures > pure substances except when going down in phase
Between substances in same phase, heavier or more atoms = more entropy
In reactions in same phase, making more molecules = more entropy
Increase temp, increase entropy; decrease pressure, increase entropy

Relationships
H
+
+
-

S
+
+
-

K
>>1
>1
1
<1
<<1

G
+ve at low temp, -ve at high temp
always +ve
always -ve
-ve at low temp, +ve at high temp

very negative
negative
0
positive
very positive

Equations:
COMMON TO ALL
Hreaction

[Hf(products)] [Hf(reactants)]
Hf of elements in natural state = 0

Sreaction

[Sf(products)] [Sf(reactants)]

Greaction

[Gf(products)] [Gf(reactants)]
Gf of elements in natural state = 0

Can combine reactions to get overall one:

Overall S or H or G from same combination of individual values
ENTROPY RELATED
H = -TS(surroundings)
S(universe) = S(reaction) + S(surroundings)
G = -TS(universe)
DELTA G RELATED
G = H - TS

(T in K; get ALL quantities in either Joules or Kilojoules)

G = -RTlnK

(R = 8.314; T in K; G in JOULES)

(G refers to energy change going from all things in standard state to equilibrium)
G = G + RTln Q
(G refers to energy change for ANY stage of reaction)
Temperature at which reaction goes from spontaneous to non-spontaneous:
G = 0; T = H/S (BOTH EITHER IN JOULES OR KILOJOULES!)