Chemical Equilibium - If K « 1→ favors reactants (mengarah ke reaktan / dominan reaktan)

-
Equilibrium
The Concept of Equilibrium
- Equilibrium is a state in which there are no observable changes as time goes
- Chemical equilibrium occurs when a reaction
by.
and its reverse reaction proceed at the same
- Chemical equilibrium is achieved when:
rate.
o the rates of the forward and reverse reactions are equal
o the concentrations of the reactants and products remain constant
 There are two types of equilibrium: Physical and Chemical.
Law of Mass Action
 Physical Equilibrium
- Law of Mass Action- For a reversible reaction at equilibrium and constant
H20 (l) ↔ H20 (g)
temperature, a certain ratio of reactant and product concentrations has a
 Chemical Equilibrium
constant value (K).
N2O4 (g) ↔ 2NO2
- The Equilibrium Constant (K)- A number equal to the ratio of the equilibrium
Physical Equilibrium
concentrations of products to the equilibrium concentrations of reactants each
- Liquid water in equilibrium with its vapor. The number of water molecules
raised to the power of its stoichiometric coefficient.
leaving the liquid is equivalent to those returning to the liquid.
- For the general reaction:
Chemical Equilibrium
aA(g) + bB(g) ↔ cC(g) + dD(g)
- Reversible reaction between nitrogen dioxide and
[𝐶]𝑐 [𝐷]𝑑
dinitrogen tetroxide forms an orange colored product. K=
[𝐴]𝑎 [𝐵]𝑏
Nitrogen dioxide is colorless and dinitrogen tetroxide is Equilibrium Constant
brown. N2O4 (g) ↔ 2NO2 (g)
- Brown forms immediately, followed by the color
lightening due to reverse reaction occurring.
N2O4 (g) ↔ 2NO2 (g)
a) initially only NO2
b) Initially only N2O4
c) Mixture Equilibrium always
occurs and at app. The same
time.
- Chemical equilibrium is defined by K. The Reaction Quotient (Q)
- The magnitude of K will tell us if the equilibrium - To calculate Q, one substitutes the initial concentrations on reactants and
reaction favors the reactants or the products. products into the equilibrium expression.
- If K » 1 → favors products (mengarah ke produk / - Q gives the same ratio the equilibrium expression gives, but for a system that
dominan produk saat equilibrium) is not at equilibrium.
- If Q = K → The system is at equilibrium.
- If Q > K → There is too much product and the equilibrium shifts to the left. - The equilibrium constant Kp for the reaction is 158 at 1000K. What is
- If Q < K → There is too much reactant and the equilibrium shifts to the right. the equilibrium pressure of O2 if the PNO = 0.400 atm and PNO = 0.270
Equilibrium Constant Expressions atm?
2
- Equilibrium constants can be expressed using Kc or Kp. 𝑃𝑁𝑂 𝑃𝑂2
Kp = 2
𝑃𝑁𝑂
- Kc uses the concentration of reactants and products to calculate the eq. constant. 2
2
𝑃𝑁𝑂
- Kp uses the pressure of the gaseous reactants and products to calculate the eq. 𝑃𝑂2 = Kp 2
2
𝑃𝑁𝑂
constant.
0,4002
- Equilibrium Constant Equations : 𝑃𝑂2 = 158 x 0,2702
= 347 atm
aA(g) + bB(g) ↔ cC(g) + dD(g) - Consider the following equilibrium at 295 K:
2
[𝑁𝑂2 ]2 𝑃𝑁𝑂 2 NH4HS(s) ↔ NH3(g) + H2S(g)
Kc = Kp =
[𝑁2 𝑂4] 𝑃𝑁2 𝑂4 - The partial pressure of each gas is 0.265 atm. Calculate Kp and Kc for
- Relationship between Kc and Kp the reaction.
Kp = 𝐾𝑐 (𝑅𝑇)∆𝑛 Kp = 𝑃𝑁𝐻3 𝑃𝐻2 𝑆 = 0.265 x 0.265 = 0.0702
∆n = moles of gaseous products – moles of gaseous reactants Kp = 𝐾𝑐(𝑅𝑇)∆𝑛
= (c + d) – (a + b) Kc= 𝐾𝑝(𝑅𝑇)−∆𝑛
Homogeneous Equilibrium ∆n = 2 – 0 = 2 T = 295 K
- Homogeneous Equilibrium- applies to reactions in which all reacting Kc = 0.0702 x (0.0821 x 295)-2 = 1.20 x 10-4
species are in the same phase. Heterogeneous Equilibrium
N2O4 (g) ↔ 2NO2 (g) - Heterogeneous Equilibrium- results from a reversible reaction
2
[𝑁𝑂2 ]2 𝑃𝑁𝑂 2 involving reactants and products that are in different phases.
Kc = [𝑁2 𝑂4 ]
Kp = 𝑃𝑁2 𝑂4 - Can include liquids, gases and solids as either reactants or products.
In most cases : Kc ≠ Kp - Equilibrium expression is the same as that for a homogeneous
Equilibrium Constant Calculations equilibrium.
- The equilibrium concentrations for the reaction between carbon - Omit pure liquids and solids from the equilibrium constant expressions.
monoxide and molecular chlorine to form COCl2 (g) at 74℃ are [CO] Heterogeneous Equilibrium Constant
= 0.012 M, [Cl2] = 0.054 M, and [COCl2] = 0.14 M. Calculate the CaCO3 (s) ↔ CaO(s) + CO2(g)
equilibrium constants Kc and Kp. [CaCO3] = constant
CO(g) + Cl2(g) ↔ COCl2(g) [CaO] = constant
[𝐶𝑂𝐶𝑙2 ] 0,14
Kc = = 0,012 𝑥 0,054 = 220 Kp = 𝑃𝐶𝑂2
[𝐶𝑙2 ][𝐶𝑂]
- The concentration of solids and pure liquids are not included in the
Kp = 𝐾𝑐 (𝑅𝑇)∆𝑛
expression for the equilibrium constant
∆n = 1- 2 = -1 R = 0,0821
T = 273 + 74 = 347 K
Kp = 220 x (0,0821 x 347)-1 = 7,7
Multiple Equilibria Reaction Quotient
- Multiple Equilibria- Product molecules of one equilibrium constant are - The reaction quotient (Qc) is calculated by substituting the initial
involved in a second equilibrium process. concentrations of the reactants and products into the equilibrium
constant (Kc) expression.
A+B↔C+D
- If
C+D↔E+F
o Qc > Kc system proceeds from right to left to reach equilibrium
A+B↔E+F
o Qc = Kc the system is at equilibrium
Kc = Kc’ x Kc”
[𝐶][𝐷] [𝐸][𝐹]
o Qc < Kc system proceeds from left to right to reach equilibrium
Kc’ = [𝐴][𝐵] Kc” = [𝐶][𝐷] Calculating Equilibrium Concentrations
[𝐸][𝐹] - If we know the equilibrium constant for a reaction and the initial
Kc = [𝐶][𝐷]
concentrations, we can calculate the reactant concentrations at equilibrium.
Writing Equilibrium Constant Expression - ICE (Initial → Mula-mula, Change → Reaksi, Equilibrium → Sisa) method
- The concentrations of the reacting species in the condensed phase are Reactants Products
expressed in M. In the gaseous phase, the concentrations can be Initial (M) :
expressed in M or in atm. Change (M) :
- The concentrations of pure solids, pure liquids and solvents do not Equilibrium (M) :
appear in the equilibrium constant expressions. - At 1280ºC the equilibrium constant (Kc) for the reaction is 1.1 x 10-3. If the
- The equilibrium constant is a dimensionless quantity. initial concentrations are [Br2] = 0.063 M and [Br] = 0.012 M, calculate the
- In quoting a value for the equilibrium constant, you must specify the concentrations of these species at equilibrium.
balanced equation and the temperature. Br2(g) ↔ 2Br(g)
- If a reaction can be expressed as a sum of two or more reactions, the
equilibrium constant for the overall reaction is given by the product of Br2(g) 2Br(g)
the equilibrium constants of the individual reactions. Initial (M) : 0,063 0,012
What does the Equilibrium Constant Tell Us ? Change (M) : -x +2x
- We can: Equilibrium (M) : 0,063 – x 0,012 + 2x
[𝐵𝑟]2 [0,012+2𝑥]2
o Predict the direction in which a reaction mixture will proceed to Kc = = = 1,1 x 10-3
[𝐵𝑟2 ] 0,063−𝑥
reach equilibrium 4x2 + 0,048x + 0,000144 = 0,0000693 – 0,0011x
o Calculate the concentration of reactants and products once 4x2 + 0,0491x + 0,0000747 = 0
equilibrium has been reached ax2 + bx + c = 0
Predicting the Direction of a Reaction −𝑏±√𝑏2 −4𝑎𝑐
- The Kc for hydrogen iodide in the following equation is 53.4 at 430ºC. x=
2𝑎
Suppose we add 0.243 mol H2, 0.146 mol I2 and 1.98 mol HI to a 1.00L −𝑏±√𝑏2 −4𝑎𝑐 −0,0491 ± √(0,0491)2 −4 (4)(0,0000747)
x= 2𝑎
= 2(4)
container at 430ºC. Will there be a net reaction to form more H2 and I2
or HI? x1 = - 0,0105
H2(g) + I2(g) → 2HI(g) x2 = - 0,00178
[𝐻𝐼]2 [1,98]2 At equilibrium, [Br] = 0,012 + 2x = 0,012 + 2(-0.0105) = - 0,009 M (TM)
Kc = [𝐻 = [0,243][0,146] = 111
2 ][𝐼2 ] = 0,012 + 2x = 0,012 + 2(-0,00178) = 0,00844 M
 At equilibrium, [Br2] = 0,063 – x = 0,063 – (-0,0105) = 0,0735 M d.) Increase in FeSCN2+(aq)
= 0,063 – x = 0,063 – (-0,00178) = 0,06478 M
- Express the equilibrium concentrations of all species in terms of the initial Changes in Volume and Pressure
concentrations and a single unknown x, which represents the change in - Changes in pressure primarily only concern gases.
concentration. - Concentration of gases are greatly affected by pressure changes and volume
- Write the equilibrium constant expression in terms of the equilibrium changes according to the ideal gas law.
concentrations. Knowing the value of the equilibrium constant, solve for x. PV = nRT
- Having solved for x, calculate the equilibrium concentrations of all species. 𝑛
P =(𝑉) RT
Factors that Affect Chemical Equilibrium
- Chemical Equilibrium represents a balance between forward and reverse Change Shift in Equilibrium
reactions. Increase in Pressure Side with fewest moles
- Changes in the following will alter the direction of a reaction: Decrease in Pressure Side with most moles
o Concentration Increase in Volume Side with most moles
o Pressure Decrease in Volume Side with fewest moles
o Volume
Changes in Temperature
o Temperature
- Equilibrium position vs. Equilibrium constant
Le Châtlier’s Principle
- A temperature increase favors an endothermic reaction and a temperature
- Le Châtlier’s Principle- if an external stress is applied to a system at
decrease favors and exothermic reaction.
equilibrium, the system adjusts in such a way that the stress is partially offset
Change Endotherm Reaction Exotherm Reaction
as the system reaches a new equilibrium position.
Increase T K decreases K increases
- Jika suatu tekanan eksternal diberikan kepada suatu sistem yang setimbang,
Decrease T K increases K decreases
maka sistem akan menyesuaikan diri sedemikian rupa untuk mengimbangi
- Consider : N2O4(g) ↔ 2NO2(g)
sebagian tekanan (stress) ini pada saat sistem mencoba setimbang kembali.
- The forward reaction absorbs heat; endothermic
- Tekanan → perubahan konsentrasi, tekanan, volume atau suhu yang menggeser
heat + N2O4(g) ↔ 2NO2(g)
sistem dari keadaan setimbangnya.
- So the reverse reaction releases heat; exothermic
Changes in Concentration
2NO2(g) ↔ N2O4(g) + heat
Change Shift in Equilibrium
Increase in (products) Left
Decrease in (products) Right
Increase in (reactants) Right
Decrease in (reactants) Left

FeSCN2+(aq) ↔ Fe3+(aq) + SCN-(aq)

a.) Solution at equilibrium
b.) Increase in SCN-(aq)
c.) Increase in Fe3+(aq)