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شبتر خمسة كيمياء
شبتر خمسة كيمياء
االتزان الديناميكى
فى العمليات
1
االتزان الديناميكي في العمليات
System
Input Output
A B C
Steady state
(Surrounding change but no net change in the system)
A B C
Dynamic equilibrium
(No net change in the system or surroundings)
A B C
Static equilibrium
2
(No change at all)
Dynamic Equilibrium
7
ب -التأثير المباشر لتركيز المواد المتفاعلة :
سرعة أي تفاعل كيميائي تتناسب مع حاصل ضرب الكتل الفعالة .1
للمواد الداخلة في هذا التفاعل
وعند سريان التفاعل الى حد معين فان المواد الناتجة تبدأ في .2
التفاعل بعضها في االتجاه المعاكس
وبالتالي تكون سرعة التفاعل او معدلة يتناسب مع حاصل ضرب .3
الكتل الفعالة للمواد الناتجة
وبعد فترة زمنية معينة يصبح معدل التفاعل في االتجاه األمامي مساو .4
لمعدله في االتجاه العكسي وهنا يقال ان التفاعل في حالة اتزان
8
Le Chatelier’s Principle
Le Chatelier’s principle states that:
energy
being used up itself.
with catalyst
time
A catalyst increases the rate of the forward and backward
reactions equally.
It does not affect the position of equilibrium, the yield or the value
of the equilibrium constant.
It does, however, increase the speed at which equilibrium is
achieved.
For the chemical system in equilibrium,
aA + bB cC + dD
15
Equilibrium constant and reaction quotient
aA + bB cC + dD
Equilibrium
constant
c
[C] [D] d
Reaction Qc
quotient a
[A] [B]b
aA + bB cC + dD
Equilibrium
constant
c
[C] [D] d
Reaction Qc
quotient [A] a [B]b
Qc = Kc
the system is at equilibrium
aA + bB cC + dD
Equilibrium
constant
c
[C] [D] d
Reaction Qc
quotient [A] a [B]b
Qc < Kc
the system is NOT at equilibrium
The reaction proceeds from left to right
until Qc = Kc.
aA + bB cC + dD
Equilibrium
constant
c
[C] [D] d
Reaction Qc
quotient [A] a [B]b
Large Kc
The forward reaction is more complete
The equilibrium position lies to the right.
The equilibrium mixture is richer in the substances on the
R.H.S. of the equation.
More expressions for reaction quotients
[H2O]2
2 H2 + O2 2 H2O Q = —————
[H2]2 [O2]
[H2]2 [O2] 1
Q r = ————— = 2 H2O 2 H2 + O2
—— [H2O]2 Q
[H2O]4
4 H2 + 2 O2 4 H2O Q2 = ————— = Q 2
[H2]4 [O2]2
Q=Q2
Note the relationships
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Equilibrium constant - mass action law
When a chemical reaction in a closed system is at equilibrium, the
reaction quotient is defined as the equilibrium constant, K, which
depends on T. For a chemical reaction in a closed system,
aA+bB cC+dD
then
[C]c [D]d
Q = —————— = K (at equilibrium)
[A]a [B]b
Units of K depends on units of [ ]s, M(a+b-c-d) if M is used.
25
Gibbs free energy, G or G
Following the definition of entropy S, Gibbs defined a function
together with enthalpy of change, H.
G=H–TS now called Gibbs free energy.
or G = H – T S for differences of these quantities
Since H is negative and S is positive for spontaneous change, Gibbs
free energy is negative for all spontaneous changes, and it unified
enthalpy and entropy for changes. Gibbs free energy is the
maximum amount of available energy in any change.
Similar to Ho, Go is the Gibbs free energy at the standard T and P.
26
Energy and equilibrium constant K
A quantity called Gibbs free energy, DG, is defined as the maximum
amount of energy from a chemical reaction for doing work.
DG is negative for spontaneous reaction
DG is positive for non-spontaneous reaction
The DG is related to the reaction quotient Q,
DG = DGo + R T ln Q
When a system is at equilibrium there is no available energy,
DG = DGo + R T ln K = 0
Thus,
DGo = – R T ln K, ln K = – DGo / R T
K = exp (– DGo / R T)
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More expressions for equilibrium constant
Note these relationships in light of ln K = – DGo / R T
[H2O]2
2 H2 + O2 2 H2O K = —————
[H2]2 [O2]
[H2]2 [O2] 1
K r = ———— = —— 2 H2O 2 H2 + O2
[H2O] 2 K
[H2O]4
K2 = ————— = K 2
4 H2 + 2 O2 4 H2O
[H2]4 [O2]2
K2=K
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An Example
Hydrogen iodide, HI, decomposes,
2 HI H2 + I2
The amount of I2 can be determined from the intensity of the
violet color of I2. When 4.00 mol of HI was placed in a 5.00-L
vessel at 458oC, the equilibrium mixture was found to contain
0.442 mol I2.
What is the value for K for the decomposition of HI at this
temperature?
29
Analysis of Example
Hydrogen iodide, HI, decomposes,
2 HI H2 + I2
The amount of I2 can be determined from the intensity of the violet
color of I2. When 4.00 mol of HI was placed in a 5.00-L vessel at
458oC, the equilibrium mixture was found to contain 0.442 mol I2.
What is the value for K for the decomposition of HI at this
temperature?
Kp
PC PD
c d
PA PB
a b
Relationship between Kc and Kp
PV = nRT
n
P RT = [Gas]RT
V
At fixed T, P [Gas]
Consider the equilibrium system :
c d
PC PD
Kp a b
PA PB
[C]c (RT)c [D]d (RT) d
[A] a (RT) a [B]b (RT)b
If a + b = c + d, Kp = Kc