‫الفصل الخامس‬

‫االتزان الديناميكى‬
‫فى العمليات‬

‫‪MIC EQUILIBRIUM IN PROCE‬‬

‫‪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

No change in the position

of the girl

An example of dynamic equilibrium

 ‫‪ 5-2‬حالة االتزان ومعدل التفاعل ‪:‬‬

‫• ‪  ‬حالـة االتزان تعنـى ان معدل التفاعـل فـى اتجاه معين‬

‫يساوى نفس المعدل في االتجاه المعاكس‬

‫• معدل التفاعـل فـي كثيـر مـن الحاالت يساوى معدل‬

‫ابطا خطوة في هذا التفاعل‬
‫‪4‬‬
Q.4 (i)
H2(g) + I2(g) 2HI(g)

Time taken to reach

the equilibrium
state
 ‫‪ 5-3‬العوامل التى تؤثر على االتزان الكيميائى‬
‫يتاثـر التفاعـل الكيميائـي فـى منظومـة مـا فـى حالة اتزان‬
‫على العديد من العوامل منها ‪-:‬‬
‫درجة الحرارة‬
‫التغير في التركيز‬
‫ج‪ -‬العوامل المساعدة‬
‫وتؤثر هذه العوامل على االتزان النهائي بطريقتين ‪:‬‬
‫‪ .1‬السرعة التي يصل بها التفاعل الى مرحلة االتزان‬
‫‪ .2‬النسـبة بيـن تركيـز ناتـج التفاعـل وتركيز المواد‬
‫المتفاعلة بعد الوصول الى مرحلة االتزان‬
‫‪6‬‬
 ‫أ‪ -‬التاثير المباشر لدرجة الحرارة ‪:‬‬
‫في التفاعالت الماصة للحرارة‬
‫سرعه التفاعـل تزداد بارتفاع درجة الحرارة وبالتالـي فان رفع درجة‬
‫الحرارة يزيد من سرعه الوصول الى مرحلة االتزان‬
‫والعكسـ صحيح للتفاعالت الطاردة للحرارة‪.‬‬

‫‪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:

If a factor affecting the

position of an equilibrium is
altered, the position of the
equilibrium shifts to oppose
the effect of the change.

Le Chatelier’s principle is used to

determine what effect a change will
have on a mixture at equilibrium.
Effect of temperature on Kc
Changing the temperature changes the value
of the equilibrium constant, Kc.

The effect on Kc depends on whether the reaction

is exothermic or endothermic.

 If the reaction is exothermic, increasing the

temperature shifts the equilibrium to the left
and the value of Kc decreases.

 If the reaction is endothermic, increasing the

temperature shifts the equilibrium to the right
and the value of Kc increases.
Effect of concentration on Kc
The value of the equilibrium constant is only affected
by temperature.

If the concentration of a reactant or product changes, the

equilibrium shifts to oppose the change.
 If the concentration of a product is decreased, the
equilibrium shifts to convert more of the reactants into
products.
 If the concentration of a reactant is decreased, the
equilibrium shifts to favour the backward reaction.
The ratio of products to reactants is restored and the value of Kc
remains the same.
The effect of pressure
The effect of a catalyst
A catalyst increases the
rate of reaction without without
catalyst

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

Equilibrium constant expressed

in concentration
Kc depends on temperature and the
nature of reaction
 ‫ج – تأثير العوامل المساعدة‪:‬‬

‫العديد من التفاعالت الكيميائية يتأثر بدرجة كبيرة‬

‫ببعض االضافات سواء لتثبيط او زيادة معدل التفاعل‬
‫وال يعتد بتأثيرها في حساب ثابت االتزان ويطلق على‬
‫هذه المواد العوامل المساعدة ويمكن تعريف المادة‬
‫المساعدة على انها تلك المادة التي تؤثر على سرعة‬
‫التفاعل دون احداث أي تغيير في ناتج التفاعل‬

‫‪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
20
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.

If Q < K, the reaction goes forward | to increase [product]

if Q = K, the system is at equilibrium |the law of mass action
if Q > K, the reaction goes backward | to decrease [product]
21
Evaluating K
The equilibrium mixture is found to contain 0.07, 0.11, 0.03
and 0.03 moles of CO, H2, CH4 and H2O respectively for the
reaction:
CO (g) + 3 H2 (g)  CH4 (g) + H2O (g)
What is the equilibrium constant, K?
Solution
CO (g) + 3 H2 (g)  CH4 (g) + H2O (g)
start 0.07 0.11 0.03 0.03
(0.03) (0.03)
K = —————— = 9.7
(0.07) (0.11)3
What governs the quantitative relationship among
equilibrium mixtures?
22
Evaluate quantities
When 0.10 moles CO and 0.20 moles of H2 are placed in a
1-L vessel at temperature T and allowed to come to
equilibrium. The mixture is found to contain 0.03 moles
H2O for the reaction:
CO (g) + 3 H2 (g)  CH4 (g) + H2O (g)
What is the equilibrium constant, K?
Solution (note the strategy please)
CO (g) + 3 H2 (g)  CH4 (g) + H2O (g)
start 0.10 0.20 0 0
change - x - 3x +x +x (x=0.03)
eqlbm 0.1-x 0.2-3x 0.03 0.03
[ ] 0.07 0.11 0.03 0.03
K = (0.03) (0.03) / (0.07) (0.11)3 = 9.7
23
Evaluate quantities
When 0.08 moles CO, 0.14 moles of H2, and 0.08 moles of
CH4 are placed in a 1-L vessel at temperature T and allowed
to come to equilibrium. The mixture is found to contain 0.01
moles H2O for the reaction:
CO (g) + 3 H2 (g)  CH4 (g) + H2O (g)
What is the equilibrium constant, K?
Solution (note the strategy please)
CO (g) + 3 H2 (g)  CH4 (g) + H2O (g)
start 0.08 0.14 0.08 0
change - x - 3x 0.08+x +x (x=0.01)
eqlbm 0.08-0.01 0.14-0.03 0.08+0.01 0.01
[ ] 0.07 0.11 0.09 0.01
K = (0.09) (0.01) / (0.07) (0.11)3 = 9.7
24
Entropy
We all know that heat flow from a high-T object into a low-T
object. This type of change can be described as due to increase of
entropy.
Entropy S is the amount of energy transferred, E, divided by T.
E
S = ———— or T S = E
T
Entropy increases for spontaneous changes (reactions).
Entropy is also associated with randomness of ordering.

What causes change when no apparent energy is involved?

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.

What drives physical and chemical changes?

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)

27
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
28
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?

Analysis of the problem:

[HI]0 = 4.0 mol / 5.00 L = 0.800 M
[I2]equilibrium = 0.442 mol / 5.0 L = 0.0884 M
Know your strategy 
30
 Calculate Kc
Example 14.3 The equilibrium concentration of various species are
given below their symbols,
2 HI (g) = H2 (g) + I2 (g)
start 0.800 0 0
change =? = ? = 0.0884 M from experiment
equlbm 0.800-2x x x
value 0.6232 0.0884 0.0884 M
0.0884*0.0884
Kc = ——————— = 0.0201
(0.6232)2
Skill: re-interpret question. Evaluate other quantities and K from known
start conditions and experimental results
Evaluate DGo 31
 Equilibrium
Constant in Terms
of Partial Pressures
For gaseous systems in dynamic equilibria,
it is more convenient to express the equilibrium constants in
terms of partial pressures.

aA(g) + bB(g) cC(g) + dD(g)

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 :

aA(g) + bB(g) cC(g) + dD(g)

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

 Kc (RT)(c d) (a b)

If a + b = c + d, Kp = Kc