Termodinamika

Kesetimbangan Kimia
Kespontanan Reaksi Kimia
Dapat diramalkan dengan mengkuantifikasi nilai ∆Gr (Energi Gibss).
Deskripsi Kesetimbangan Kimia
Key points
(a) The reaction Gibbs energy depends logarithmically on the reaction
quotient. When the reaction Gibbs energy is zero the reaction quotient has a
value called the equilibrium constant.
(b) The results are readily extended to a general reaction. (c) Under ideal
conditions, the thermodynamic equilibrium constant may be approximated
by expressing it in terms of concentrations and partial pressures.
(d) The presence of the enthalpy and entropy contributions to K are related to
the role of the Boltzmann distribution of molecules over the available states.
(e) The biological standard state is defined at pH = 7.
Gas Ideal
•A   B

ΔGr = ΔGor + RT lnQ

ΔGr = ΔG0f(B) − ΔGof(A)

Jika ΔGr =0, maka harga Q terkuantifikasi menjadi harga K.

0 = ΔGor + RT lnK K
Reaksi Umum
•ΔG
  r = ΔGor + RT lnQ

ΔGr = ΔG0f(B) − ΔGof(A)

Jika ΔGr =0, maka harga Q terkuantifikasi menjadi harga K.

0 = ΔGor + RT lnK K
RT ln K = − ΔGor
Example
• Calculate the equilibrium constant for the ammonia synthesis
reaction, N2(g) +3 H2(g) (eq.) NH3(g), at 298 K and show how K is
related to the partial pressures of the species at equilibrium when the
overall pressure is low enough for the gases to be treated as perfect.
ΔG0f(NH3,g) = −16.5 kJ mol−1
Self test. 1
• Evaluate the equilibrium constant for N2O4(g) (eq.) NO2(g) at 298 K.
[K = 0.15]
Example 6.2
• The degree of dissociation (or extent of dissociation, α) is defined as
the fraction of reactant that has decomposed; if the initial amount of
reactant is n and the amount at equilibrium is neq, then α = (n −
neq)/n. The standard reaction Gibbs energy for the decomposition
H2O(g)→H2(g) + O2(g) is +118.08 kJ mol−1 at 2300 K. What is the
degree of dissociation of H2O at 2300 K and 1.00 bar?
Self test 2
• Given that the standard Gibbs energy of reaction at 2000 K is +135.2
kJ mol−1 for the same reaction, suppose that steam at 200 kPa is
passed through a furnace tube at that temperature. Calculate the
mole fraction of O2 present in the output gas stream.
Respon Kesetimbangan akibat Perubahan
Kondisi
Henry Le Chatelier (1850-1936) berpendapat bahwa jika pada kesetimbangan kimia dilakukan gangguan, maka
akan terjadi pergeseran kesetimbangan, tetapi sistem akan berusaha mempertahankan kesetimbangan tersebut
sehingga pengaruhnya menjadi sekecil mungkin.

*) Perubahan tekanan
Jika tekanan sistem diperbesar, maka kesetimbangan akan bergeser ke arah zat yang memiliki jumlah mol
(koefisisen) lebih kecil, dan sebaliknya.

*) Perubahan Suhu
Apabila suhu dinaikkan, maka reaksi akan bergeser ke arah reaksi yang memerlukan panas (endoterm).
Sebaliknya, jika suhu diturunkan, maka reaksi akan bergeser ke arah reaksi yang mengeluarkan panas
(eksoterm).
Ramalkan pergeseran kesetimbangan dr
reaksi berikut
Tentukan pergeran akibat daria) tekanan yang diperbesar b) suhu yang
dinaikan
a) 2SO2(g)  + O2(g)   ⇌  2SO3(g)  + kalor

b) 2NO2(g)  ⇌ N2O4(g)  + energi

c) 2HI(g)  ⇌  I2(g) + H2(g)

 d) PCl5(g)   ⇌  PCl3(g)  + Cl2(g)   - energi

Practice!
Bagaimana pengaruh kesetimbangan jika pada sistem tersebut dilakukan :
a.       Penambahan Cl2
b.      Tekanan dinaikkan
c.       Panas diturunkan
d.      Konsentrasi PCl3 diperkecil

PCl5(g)   ⇌  PCl3(g)  + Cl2(g)   - energi

Perubahan tekanan
Nilai K tidak bergantung pada perubahan tekanan.
Namun, jumlah konsentrasi masing-masing spesi bergantung pada tekanannya.

2SO2(g)  + O2(g)   ⇌  2SO3(g) 

PCl5(g)   ⇌  PCl3(g)  + Cl2(g) 

Perubahan Suhu
Persamaan Van’t Hoff
Example
The data below show the temperature variation of the equilibrium constant of the reaction
Ag2CO3(s)(eq.) Ag2O(s) + CO2(g).
Calculate the standard reaction enthalpy of the decomposition.
Practice!
The equilibrium constant of the reaction
2 SO2(g) +O2(g)(eq.)2 SO3(g)
is 4.0 × 1024 at 300 K, 2.5 × 1010 at 500 K, and 3.0 × 104 at 700 K. Estimate the reaction
enthalpy at 500 K!
Example
To estimate the equilibrium constant for the synthesis of ammonia at 500 K from its value at 298 K (6.1 × 10 5 for the reaction
N2(g) +3 H2(g) (eq.) NH3(g)), we use the standard reaction enthalpy, which can be obtained in the Data section by using ΔrHo
= 2ΔfHo(NH3,g), and assume that its value is constant over the range of temperatures. Then, with ΔrHo = −92.2 kJ mol−1we find

It follows that K2 = 0.18, a lower value than at 298 K, as expected for this exothermic
reaction.

*) The equilibrium constant for N2O4(g)(eq.) 2 NO2(g) was calculated in Estimate its value at 100°C.