Kespontanan Reaksi dan Entropi

Kimia Anorganik Fisik Latifah, MSi. Kimia FMIPA UNNES 24 September 2010

Kespontanan
spontaneous

nonspontaneous

Spontaneous reaction = having the potential to proceed without assistance of external agency

Kespontanan Reaksi

Termasuk Reaksi spontan ???

Reaksi : Fe + O2 Fe2O3
Reaksi spontan ?? Dua faktor yang menentukan terpisahnya atom-atom reaktan dan penataulangannya menjadi produk Kekuatan ikatan Derajat ketidakteraturan pada keadaan akhir

Fungsi Termodinamik : Gibbs Energy

Energi yang tersedia untuk melakukan kerja

Free Energy Change

The free energy change (DG) for a process at constant temperature and pressure is given by the Gibbs equation DGsys = DHsys T.DSsys If DG < 0 (negative), a process is spontaneous. If DG > 0 (positive), a process is nonspontaneous. If DG = 0, the process is at equilibrium.
EOS

Factors Determining DG
Free energy change depends on
enthalpy entropy

DH = (enthalpy of products) - (enthalpy of reactants) DS = (entropy of products) - (entropy of reactants) DG = DH - TDS

Enthalpy
DHo = heat released or absorbed during a chemical reaction at standard conditions. Exothermic, (-DH), heat is released. Endothermic, (+DH), heat is absorbed. Reactions favor products with lowest enthalpy (strongest bonds).

Entropy
DSo = change in randomness, disorder, freedom of movement. Increasing heat, volume, or number of particles increases entropy. Spontaneous reactions maximize disorder and minimize enthalpy. In the equation DGo = DHo - TDSo the entropy value is often small. =>

Criterion for Spontaneous Change

EOS

Signs of Thermodynamic Values

Enthalpy (H) Entropy (S) Gibbs Free Energy (G) Negative Exothermic Less disorder Spontaneous Positive Endothermic More disorder Not spontaneous

Standard Free Energy and Temperature

If DH < 0 and DS > 0, then DG is always negative(spontaneous.) If DH > 0 and DS < 0, then DG is always positive(nonspontaneous)

If DH < 0 and DS < 0, then DG is negative at low temperatures.

If DH > 0 and DS > 0, then DG is negative at high temperatures. NOTE: Even though a reaction has a negative DG it may occur too slowly to be observed

Principles of Entropy
1. The gaseous state is more probable than liquid state, which in turn is more probable than the solid state

Entropy and Temperature

S increases slightly with T

S increases a large amount with phase changes

Entropy of Various Substances at 25C

Substance
Na

Solid
12,3

Liquid
13,83

Gas
36,71

P Si Pb H2O

9,82 4,43 15,5 -

10,28 11,21 17,14 16,72

38,98 40,12 41,89 45,14

2. A monoatomic gas is more probable than polyatomic moleculer gas, and hence tends to have higher entropy H 27,4 H2 15,6

N 36,6 O 38,5 F 37,9 Si 40,1 P 39,0 S 40,1

N2 22,9 O2 24,5 F2 24,4 Si2 17,5 P2 26,1 S2 27,3

O3 19,0

P4 16,7 S8 12,9

3. An amorphous solid is more probable than a crystalline solid, and a simple crystalline solid more probable than a more complex crystalline solid

4. Coordination complex is less probable than its separete components

5. Compounds of elements of higher atomic weight, or molecules of the free elements themselves, tend to have higher entropy Effect of Mass on entropy of Gases at 25C :
X HX NaX PbX2 ZrX4 F 41,51 51,70 69,35 76,95 Cl 44,65 54,88 76,63 87,37 Br 82,43 98,78 I 85,91 108,42

Standard Molar Entropies

5. In general, the more atoms in its molecules, the greater is the entropy of a substance Entropy is a function of temperature

EOS

6. At ordinary temperature, entropy effects are commonly small enough to have relatively little effect on the direction of reaction unless the difference in total bonding energy between reactants and products is relatively small 7. All chemical reactions that increase the entropy occur spontaneously at high enough temperature DG = DH T.DS