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• What is equilibrium?
• Expressions for equilibrium constants, Kc;
• Calculating Kc using equilibrium concentrations;
• Calculating equilibrium concentrations using initial
concentration and Kc value;
• Relationship between Kc and Kp;
• Factors that affect equilibrium;
• Le Chatelier’s Principle
What is Equilibrium?
This is not Equilibrium?
Chemical Equilibrium in Nature:
(The formation of stalagmites and Stalactites)
Chemical Equilibrium
• Consider the following reactions:
CaCO3(s) + CO2(aq) + H2O(l) Ca2+(aq) + 2HCO3-(aq) ..(1)
and
Ca2+(aq) + 2HCO3-(aq) CaCO3(s) + CO2(aq) + H2O(l) ..(2)
• Examples:
[NH 3 ] 2
N2(g) + 3H2(g) ⇄ 2NH3(g); Kc = [N 2 ][H 2 ]3
[PCl 3 ][Cl 2 ]
PCl5(g) ⇄ PCl3(g) + Cl2(g); Kc = [PCl 5 ]
[CO][H 2 ]3
Kc =
[CH 4 ][H 2 O]
Calculating Equilibrium Constant
• Example-1:
1.000 mole of H2 gas and 1.000 mole of I2 vapor are
introduced into a 5.00-liter sealed flask. The mixture is
heated to a certain temperature and the following reaction
occurs until equilibrium is established.
H2(g) + I2(g) ⇄ 2HI(g)
At equilibrium, the mixture is found to contain 1.580 mole
of HI. (a) What are the concentrations of H2, I2 and HI at
equilibrium? (b) Calculate the equilibrium constant Kc.
Calculating Equilibrium Constant
for reaction: H2(g) + I2(g) ⇄ 2HI(g)
• ————————————————————————————
• H2(g) + I2(g) ⇄ 2 HI(g)
• ————————————————————————————
• Initial [ ], M: 0.200 0.200 0.000
• Change in [ ], M: -0.158 -0.158 + 0.316
• Equilibrium [ ], M 0.042 0.042 0.316
• ————————————————————————————
[HI] 2 (0.316) 2
Kc = = 2
= 57
[H 2 ][I 2 ] (0.042 )
Calculating Equilibrium Constant
• Example-2:
0.500 mole of HI is introduced into a 1.00 liter sealed flask
and heated to a certain temperature. Under this condition
HI decomposes to produce H2 and I2 until an equilibrium is
established. An analysis of the equilibrium mixture shows
that 0.105 mole of HI has decomposed. Calculate the
equilibrium concentrations of H2, I2 and HI, and the
equilibrium constant Kc for the following reaction:
H2(g) + I2(g) ⇄ 2HI(g),
Calculating Equilibrium Constant
• aA + bB ⇄ cC + dD
where A, B, C, and D are all gases, and a, b, c,
and d are their respective coefficients,
• Kp = Kc(RT)Dn
and Dn = (c + d) – (a + b)
(In heterogeneous systems, only the coefficients
of the gaseous species are counted.)
Relationship between Kc and Kp
• For other reactions:
• 1. 2NO2(g) ⇄ N2O4(g); Kp = Kc(RT)-1
• 2. H2(g) + I2(g) ⇄ 2 HI(g); Kp = Kc
• 3. N2(g) + 3H2(g) ⇄ 2 NH3(g); Kp = Kc(RT)-2
Homogeneous & Heterogeneous Equilibria
Homogeneous equilibria:
CH4(g) + H2O(g) ⇄ CO(g) + 3H2(g);
CO(g) + H2O(g) ⇄ CO2(g) + H2(g);
Heterogeneous equilibria:
CaCO3(s) ⇄ CaO(s) + CO2(g);
HF(aq) + H2O(l) ⇄ H3O+(aq) + F-(aq);
PbCl2(s) ⇄ Pb2+(aq) + 2 Cl-(aq);
Equilibrium Constant Expressions for
Heterogeneous System
• Examples:
CaCO3(s) ⇄ CaO(s) + CO2(g);
Kc = [CO2] Kp = PCO2; Kp = Kc(RT)
[B][F]
Eqn(2): C + E ⇄ B + F; K2
[C][E]
Combining Equations and Equilibrium Constants
• Net equation: A + E ⇄ D + F;
[D][F]
K net = K1 x K2
[A][E]
[HI] 2 (2 x ) 2
Kc 2
55.6
[H 2 ][ I 2 ] (0.100 - x )
Calculation of equilibrium concentrations
2x
55.6 7.46
(0.100 - x
2 x 0.746 - 7.46 x; 9.46 x 0.746
x 0.0789 ;
[H 2 ] [I 2 ] 0.0211 M; [HI] 0.158 M
Equilibrium Exercise #6
(Answer: PNO2 = 1.06 atm; PN2O4 = 1.43 atm; Ptotal = 2.49 atm)
Equilibrium Exercise #7
The reaction:
PCl5(g) ⇄ PCl3(g) + Cl2(g) has Kc = 0.0900.
A 0.1000-mol sample of PCl5 is placed in an empty
1.00-L flask and the above reaction is allowed to
come to equilibrium at a certain temperature. How
many moles of PCl5, PCl3, and Cl2, respectively, are
present at equilibrium?